Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
1998-04-22
2001-08-21
Hoke, Veronica P. (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
active
06277912
ABSTRACT:
TECHNICAL FIELD OF THE INVENTION
This invention relates to less polluting or non-polluting, aqueous, chlorinated polyolefin-based resin compositions which are used as a primer or a coating composition for moldings or films consisting mainly of polyolefin resins, such as polypropylene, ethylene-propylene copolymers, and ethylene-propylene-butene copolymers. More detailedly explaining, this invention provides an aqueous, chlorinated polyolefin-based resin composition and a method of its manufacture, which resin composition, when used as a primer or a base coat for moldings or films of polyolefin-based resins, forms a coating film having a good adhesiveness to the polyolefin base material and also a good interlayer adhesiveness to the base coat and/or the top coat, and having good gasohol resistance, moisture resistance, impact resistance, and flexibility. When the composition is used as a single-coat material, it gives a coating film having a good adhesiveness to the polyolefin base material, and has a good miscibility or compatibility with polymer emulsions and pigments used in combination with it, and in addition keeps the physical properties of the coating film after exposure. In addition to the use as an adhesive as mentioned above, the resin composition is used for inks, coating materials, their primers, etc.
BACKGROUND OF THE INVENTION
Polyolefin resins are relatively inexpensive and have good properties such as chemicals resistance, water resistance, heat resistance, etc. Thus, they have been used as an industrial material in a wide range of applications; the use for auto parts is an example. Having those advantages, however, polyolefin resins are crystalline and have no reactive functional groups on their surface; so it has been difficult to apply adhesion and coatings to base materials of the polyolefin-based resin. To solve this problem, attempts have been made to improve the adhesiveness of coating films to polyolefin-based resins by modifying the resin surface through vapor cleaning, defatting, acid treatment, corona discharge treatment or plasma treatment. On the other hand, in the fields of the coatings, adhesives, and inks, chlorinated polyolefins, which have a relatively good adhesiveness to such hard-to-coat resin surfaces as mentioned above, have been used. However, most of those chlorinated polyolefins were of the solution type, dissolved in an organic solvent such as toluene, xylene, and/or esters. Thus, the organic solvents released into the atmosphere at the time of the coating operation gave a serious environmental and sanitary impact on coating workers and citizens living in a wide area around the coating place, and even on the surrounding ecosystem. Based on this situation, a patent application (WO9303104) has recently been made for an aqueous emulsion in which chlorinated polyolefins are blended with resins containing carboxylic acids. In these blend systems, however, a phase separation occurred between the different polymers after the formation of the coating film and the hydrophilic component, such as a surfactant came into the coating polymers, leading to the degraded strength and lowered water resistance of the coating film.
Considering what has been described above, the assignee of this patent has already completed the invention in which an aqueous emulsion is obtained by dissolving chlorinated polyolefins in monomers or oligomers and emulsifying the solution with a surfactant and then polymerizing (Japanese patent applications tokukaihei 5-209006, tokukaihei 5-287251, tokukaihei 6-287521, tokukaihei 8-176309). The object of these inventions was to increase the strength and water resistance of the coating film by copolymerization of chlorinated polyolefins with acrylic monomers to achieve the higher molecular weight. In order to achieve the polymerization as originally intended, however, the surfactant had to be selected from a narrow range and, in addition, it had to be used in a large amount. To improve the water resistance of the coating film from these chlorinated polyolefin-based resin emulsions, the use of water-soluble substances had to be further decreased.
The object of this invention is to achieve, without vapor-cleaning or defatting the surface of a polyolefin base material with chlorine-containing organic solvents such as trichloroethane, etc., a coating which has adhesiveness to a polyolefin base material and also has an improved interlayer adhesiveness to the base coat and/or the top coat and improved levels in properties such as water resistance, gasohol resistance, etc., and also which is less polluting or non-polluting.
SUMMARY OF THE INVENTION
In an attempt to solve the problem mentioned above, the inventors made a lot of effort to complete the invention. The first fruit of this invention is an aqueous, chlorinated polyolefin-based resin composition which is obtained by chlorinating, in a range of 5-50 wt. %, one or more kinds of polymers selected from polyolefins modified with the compounds (A), (B), and/or (C) below, and which has an acid value of 1-500 mg KOH/g:
(A) &agr;,&bgr;-unsaturated carboxylic acids represented by any of c, d, and e in the general formula (1,) below,
R
1
, R
2
, R
3
, R
4
and R
5
are independently selected from the group consisting of
H, CH
3
, C
2
H
5
, C
3
H
7
, C
4
H
9
, C
5
H
11
, C
6
H
13
, C
7
H
15
, C
8
H
17
, C
9
H
19
, C
10
H
21
and COOH
R
2v
is selected from the group consisting of:
CH
2
, C
2
H
4
, C
3
H
6
, C
4
H
8
, C
5
H
10
, C
6
H
12
, C
7
H
14
, C
8
H
16
, C
9
H
18
, C
10
H
20
CHCOOH, C(CH
3
)COOH, C(C
2
H
5
)COOH, C(C
3
H
7
)COOH and C(C
4
H
9
)COOH,
(B) and/or acid anhydrides of the &agr;,&bgr;-unsaturated carboxylic acids of (A) represented by either of a and b in the general formula (1) below,
R
1
′ is selected from the group consisting of:
H, CH
3
, C
2
H
5
, C
3
H
7
, C
4
H
9
, C
5
H
11
, C
6
H
13
, C
7
H
15
, C
8
H
17
, C
9
H
19
and C
10
H
21
R
2
′ is selected from the group consisting of:
H, CH
3
, C
2
H
5
, C
3
H
7
, C
4
H
9
, C
5
H
11
, C
6
H
13
, C
7
H
15
, C
8
H
17
, C
9
H
19
and C
10
H
21
R
1
″ is selected from the group consisting of:
CH
2
, C
2
H
4
, C
3
H
6
, C
4
H
8
, C
5
H
10
, C
6
H
12
, C
7
H
14
, C
8
H
16
, C
9
H
18
, C
10
H
20
, CHCOOH, C(CH
3
)COOH, C(C
2
H
5
)COOH, C(C
3
H
7
)COOH and C(C
4
H
9
)COOH,
R
2
″ is selected from the group consisting of:
H, CH
3
, C
2
H
5
, C
3
H
7
, C
4
H
9
, C
5
H
11
, C
6
H
13
, C
7
H
15
, C
8
H
17
, C
9
H
19
and C
10
H
21
(C) and/or compounds having one or more double bonds in a molecule, represented by either of a and b in the general formula (2) below.
(2)-a
CH
2
═C(R
1′″
)COOR
2
′″
R
1′″
is selected from the group consisting of:
H and CH
3
R
2′″
is selected from the group consisting of:
H, CH
3
, C
2
H
5
, C
3
H
7
, C
4
H
9
, C
5
H
11
, C
6
H
13
, C
7
H
15
, C
8
H
17
, C
9
H
19
, C
10
H
21
, C
11
H
23
, C
12
H
25
, C
13
H
27
, C
14
H
29
, C
15
H
31
, C
16
H
33
, C
17
H
35
, C
18
H
37
, C
19
H
39
, C
20
H
41
, C
2
H
4
OH, C
3
H
6
OH, C
4
H
9
OH, C
5
H
10
OH, C
6
H
12
OH, C
7
H
14
OH, —CH
2
CH
2
N(CH
3
)
2
, —CH
2
CH
2
N(CH
2
CH
3
)
2
, —CH
2
CH
2
OCOCH
2
CH
2
COOH, —CH
2
CH
2
OCOC(CH
3
)═CH
2
, —(CH
2
CH
2
O)
2
COC(CH
3
)═CH
2
, —C
4
H
8
COC(CH
3
)═CH
2
, C
6
H
12
OCOC(CH
3
)═CH
2
, —CH
2
C(CH
2
═C(R
1′″
)COOCH
2
)
2
CH
2
CH
3
, —CH
2
CH(OH)CH
2
OCOC(CH
3
)═CH
2
, (CH
2
CH
2
O)
x
COC(CH
3
)═CH
2
; 1≦X≦20
R
1iv
, R
2iv
, R
3iv
, R
4iv
, and R
5iv
are independently selected from the group consisting of
H, CH
3
, C
2
H
5
, C
3
H
7
, C
4
H
9
, C
5
H
11
, C
6
H
13
, C
7
H
15
, C
8
H
17
, C
9
H
19
, and C
10
H
21
The second fruit is the aqueous, chlorinated polyolefin based resin composition described above as the first fruit, to which, after the completion of the chlorination mentioned above, an epoxy compound or its oligomer is added so that the weight ratio of the compound having one epoxy group in a molecule and/or its oligomer to the aqueous, chlorinated polyolefin-based resin comp
Ashihara Teruaki
Funasaka Tadanori
Maekawa Shoji
Orita Ryozo
Hoke Veronica P.
Toyo Kasei Kogyo Company Limited
Wenderoth , Lind & Ponack, L.L.P.
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