JPH0369951B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new and useful resin composition for paints, and its purpose is to provide coating properties for various surface treatments and internal treatments (mainly chemical treatments). It functions as a primer for so-called polyolefin materials such as untreated films, sheets, or molded products, and can also be applied in one coat.
In particular, it is an object of the present invention to provide a resin composition for coating material that has good adhesion and solvent resistance. Conventional paints made from alkyd, acrylic, or epoxy resins have little adhesion to various molded products made of crystalline polyolefins, which have low polarity. It has also been proposed to use as a primer, in particular atactic polypropylene modified with maleic anhydride or ethylene-propylene copolymer modified with maleic anhydride, but these all have poor adhesion to such materials. Although it has good properties, it also has poor interlayer adhesion with the top coat, and when used as a clear paint, the coating film becomes cloudy.On the other hand, when used as an enamel paint system containing pigments, In addition to being extremely poor in pigment dispersibility, there were problems in that the paint itself lacked stability. There is also a known coating method in which chlorinated polyolefin itself is used as a primer and acrylic resin is used for the top coat, but this method has problems with interlayer adhesion with the top coat, solvent resistance, and long-term durable adhesion. It has the disadvantage of decreasing. Furthermore, although a coating method using this chlorinated polyolefin itself as a top coat is known, the hardness, solvent resistance, and weather resistance of the coating film are significantly deteriorated, so that it is impractical. Therefore, we developed a resin composition for paint that maintains long-term adhesion to polyolefin materials, maintains interlayer adhesion with the top coat, and improves performance such as hardness and solvent resistance of the coating film. Although resin compositions composed of a chlorinated polyolefin and an acrylic (co)polymer are effective, such resin compositions have the following problems. First, when the chlorination rate exceeds 50% by weight (hereinafter abbreviated as %), the compatibility between the chlorinated polyolefin and the acrylic (co)polymer improves, but the adhesion of the formed coating film decreases. It is difficult to put it into practical use because the solvent resistance decreases, and chlorinated polyolefin with a chlorination rate of 50% or less, for example around 35%, can be used to improve adhesion, but acrylic Similarly, it is difficult to put it into practical use because it lacks compatibility with the (co)polymer and the stability of the coating material becomes extremely poor. However, as a result of intensive research aimed at further improving the compatibility between specific chlorinated polyolefins and acrylic (co)polymers, and at the same time improving the adhesion to polyolefin materials, the present inventors found that (meth)acrylic acid A vinyl (co)polymer is grafted onto a chlorinated polyolefin obtained by polymerizing a vinyl monomer containing an ester as an essential component in the presence of a specific chlorinated polyolefin with a chlorination rate of 50% or less. A mixture of a so-called chlorinated polyolefin-modified acrylic or vinyl graft copolymer in a chlorinated form and a solid resin that is compatible with the graft copolymer and has the ability to adhere to the polyolefin material, We have completed the present invention by discovering that it has extremely good compatibility and also has good adhesion ability. That is, the present invention provides acrylic ester and/or methacrylic ester (a-1) in the presence of 50% or less chlorinated polyolefin.
~100% and 0 to 50% of the other vinyl monomer (a-2) copolymerizable with these (meth)acrylic acid esters (a-1), and the above chlorinated polyolefin. , the monomers (a-1) and (a-2)
99 to 50 parts by weight of the graft copolymer (A) obtained by polymerizing so that the total solid content weight ratio with the total weight is 10:90 to 90:10; It is soluble in group hydrocarbon type, fatty acid hydrocarbon type, alicyclic hydrocarbon type, ketone type, ester type, alcohol type and chlorine type single solvent or combined solvent, and is compatible with the above graft copolymer. For paints containing as an essential component 1 to 50 parts by weight of a resin (B) with good compatibility, especially various natural resin-modified maleic acid resins, various terpene polymers, or various macron resins. A resin composition is provided. Here, the above-mentioned chlorinated polyolefin refers to one with a chlorination rate of 50% or less, preferably 10 to 40%. Typical polyolefins include tethylene, propylene, 1-butene, 3-methyl -1-butene, 3-methyl-1-
Homopolymers or copolymers of α-olefins such as hebutene, or copolymers of α-olefins with other vinyl monomers such as ethylene-vinyl acetate, ethylene-butadiene, and ethylene-acrylic acid ester. Therefore, typical examples of the chlorinated polyolefin include chlorinated polyethylene, chlorinated polypropylene, chlorinated ethylene-propylene copolymer, and chlorinated ethylene-vinyl acetate copolymer. Regarding the chlorination rate of the chlorinated polyolefin, if the chlorination rate exceeds 50%, the adhesion to the polyolefin material will decrease, so the determination of the chlorination rate is based on the adhesion, flexibility, and This should be done while taking various coating film performances such as hardness into consideration, and should preferably be set at 10 to 40%, more preferably 15 to 35%, and in this way the most balanced coating film performance can be achieved. A resin composition having the following properties is obtained. On the other hand, typical examples of the above-mentioned (meth)acrylic esters (a-1) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylate. i-Butyl acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate or (meth)acrylate
Examples include cyclohexyl acrylate,
When using these, either one type or two or more types may be used, and for the (meth)acrylic acid ester (a-1), hydroxyl group,
There is no problem even if some monomers having functional groups such as glycidyl groups or acid groups are used in combination, and copolymerization of such functional group-containing monomers improves solvent resistance and pigment dispersibility. and is especially recommended. If the amount of the (meth)acrylic ester acid (a-1) used is less than 50%,
Since the hardness and solvent resistance of the resulting coating film will be insufficient, a ratio of 50% or more is appropriate; however, if it exceeds 90%, problems will arise with respect to the adhesion of the coating film. It is preferably within the range of 50 to 90% by weight. Next, the (meth)acrylic acid ester (a
-1) and other vinyl monomers (a-
Typical examples of 2) include diesters of unsaturated dibasic acids such as styrene or dibutyl itaconate, and these monomers are used as appropriate depending on the coating performance, but the amount used should be less than 50%. Therefore, when polymerizing the above monomers in the presence of chlorinated polyolefin, the abundance ratio of chlorinated polyolefin and monomer (mixture) is 10:90.
A suitable solid content ratio is from 90:10 to 15:85 to 40:60. In addition, by polymerizing various monomer components in which these (meth)acrylic acid esters are essential in the presence of a chlorinated polyolefin component such as a pre-depleted chlorinated polyolefin component, other essential components of the composition of the present invention can be obtained. A graft copolymer (A) that has good compatibility with the solid resin (B) described below, which is a component, can be obtained, but such a polymerization method is usually carried out at a polymerization temperature of 60 to 100°C, using benzoyl peroxide. Solution polymerization is preferably carried out using a radical-generating polymerization initiator such as When the amount of chlorinated polyolefin used decreases, it is undesirable because the adhesion to polyolefin materials decreases.On the other hand, when the amount of chlorinated polyolefin used increases beyond 90:10, the resulting coating film This is not preferred because the solvent resistance is significantly reduced. The graft copolymer (A) thus obtained has excellent adhesion in a broad sense, including long-term adhesion and interlayer adhesion with the top coat.
Provides a cured coating film with excellent coating performance including solvent resistance. However, even though the graft copolymer (A) has such excellent adhesion, it cannot be used in hot water resistance tests for molded products made of specific olefinic materials, such as polypropylene homopolymer without any fillers. Later adhesion is reduced. Therefore, a solid resin that is compatible with the graft copolymer (A) and has the ability to adhere to the above-mentioned polypropylene material is added to 99 to 50 parts by weight of the graft copolymer (A). By blending it in a ratio of 1 to 50 parts by weight, preferably 10 to 40 parts by weight, it has good adhesion ability to all polyolefin materials, and in particular has excellent hot water secondary adhesion properties. Although the present inventors have learned that a cured coating film having coating performance can be obtained,
Here, typical examples of such unique resins include the following. In other words, it is solid at room temperature and is soluble in single or combined solvents of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ketones, esters, alcohols, or chlorine. The resin is compatible with the graft copolymer (A) and also has adhesion ability to various polyolefin materials, specifically, 100% carbonic acid resin, natural resin such as rosin, etc. various carbolic acid resins modified with natural resins, maleic acid resins modified with natural resins, various xylene resins, ketone resins, terpene polymers or α-pinene polymers, terpene/carbonic acid resins, various rosin resins, or various coumarons. Examples include resins, among which only representative examples include various natural resin-modified maleic acid resins, various terpene polymers, and various coumaron resins. Of course, resin (B) may be used alone or in combination of two or more. If the amount of the solid resin (B) used exceeds 50 parts by weight, the resulting coating film will have insufficient solvent resistance, so the range of 1 to 50 parts by weight is appropriate and preferred. is preferably used in a range of 10 to 40 parts by weight. The thus obtained resin composition for coatings of the present invention can be widely used for various polyolefin materials or base materials such as various molded products such as films and sheets, and can be used, for example, as a primer in coating polyolefin molded products. It can also be used as a top coat for various structures and structures, and it can also be used as a binder for printing inks, but in particular it can be used for various molded products and structures made of polyolefin. Useful for the body or structures. Thus, the composition of the present invention can be used as a coating for molded articles, structures, or structures made of homopolymers or copolymers of α-olefins such as ethylene, propylene, 1-butene, or 3-methyl-1-heptene. It can be applied particularly to polyolefin molded products containing fillers such as titanium oxide, talc, or silica, but it is also excellent for so-called additive-free polyolefin materials that do not contain such fillers. It exhibits good adhesion and can be used as a clear paint or as an enamel paint system mixed with known and commonly used additive components such as pigments and leveling agents. Next, the present invention will be specifically explained using reference examples, working examples, and comparative examples.
shall mean. Reference Example 1 [Preparation example of graft copolymer (A)] In a reactor equipped with a stirrer and a cooler,
Add 100 g of "Hardren 14LLB" (chlorinated polypropylene manufactured by Toyo Kasei Kogyo Co., Ltd.; chlorination rate = 28%, non-volatile content = 15%) and 30 g of toluene, raise the internal temperature to 80°C, and add 59.5 g of Methyl methacrylate, 25.5g i-Butyl methacrylate, 0.4g
A solution of benzoyl peroxide and 0.4 g of azobisisobutyronitrile dissolved in 35 g of toluene was removed over a period of 3 hours and kept at the same temperature for an additional 12 hours to determine the solid content (non-volatile content). but
A 40.3% chlorinated polypropylene modified acrylic resin was obtained. Hereinafter, this will be abbreviated as resin (A-1). Reference Example 2 [Preparation Example of Graft Copolymer (A)] Reference Example 1 except that the same amount of cyclohexyl methacrylate was used instead of i-butyl methacrylate.
In the same manner as above, a chlorinated polypropylene-modified acrylic resin with a nonvolatile content of 40.5% was obtained. Hereinafter, this will be abbreviated as resin (A-2). Reference Example 3 [Example of preparation of graft copolymer (A)] Instead of reducing the amount of i-butyl methacrylate to 24 g, 1.5 g of methacrylic acid was used, and benzoyl peroxide and A chlorinated polypropylene-modified vinyl copolymer having a nonvolatile content of 40.5% was obtained in the same manner as in Reference Example 1, except that the amount of azobisisobutyronitrile used was changed to 0.3 g and 0.5 g, respectively. Hereinafter, this will be abbreviated as resin (A-3). Reference Example 4 [Example of Preparation of Graft Copolymer (A)] In a reactor similar to Reference Example 1, a
406" [chlorinated polypropylene manufactured by Sanyo Kokusaku Pulp Co., Ltd.; chlorination rate = 66%, nonvolatile content = 40%] of 37.5
Add 97.5g of toluene and 97.5g of toluene, and raise the internal temperature to 80.
℃, add 0.35 g of methyl methacrylate, 25.5 g of i-butyl methacrylate and 30 g of toluene.
of benzoyl peroxide and 0.3 g of azobisisobutyronitrile were dissolved in 3
The mixture was added dropwise over a period of time and maintained at the same temperature for 12 hours to obtain a control chlorinated polypropylene-modified acrylic resin with a non-volatile content of 40.5%. Hereinafter, this will be abbreviated as resin (A'-1). Example 1 Resin (A-1) obtained in Reference Example 1, "Betsukasite 1111-60T" [natural resin-modified maleic acid resin manufactured by Dainippon Ink and Chemicals Co., Ltd.; non-volatile content = 60
%] and "Alpaste 1109MA" [Toyo Aluminum Co., Ltd. product] at a solid content weight ratio of 72:18:
Then, using a mixed solvent of xylene/n-butyl acetate = 50/50 (weight ratio) as a thinner, the viscosity was adjusted to 12 seconds using an Iwata cup to obtain a paint. Afterwards, this paint was
BC3B" (polypropylene manufactured by Mitsubishi Yuka Co., Ltd.) with a thickness of 3 mm was coated, and then forced dry at 60°C for 30 minutes. The cured coating film thus obtained had a metallic feel and good adhesion, and in addition, the cross-cut test (durable adhesion) after being left for 6 months was also good. The results of these coating film performances are summarized in Table 1. Example 2 A cured coating film was obtained in the same manner as in Example 1, except that the same amount of resin (A-2) obtained in Reference Example 2 was used instead of resin (A-1). , and conducted various performance evaluations. The results are summarized in Table 1. Example 3 Instead of resin (A-1), the same amount of resin (A-3) obtained in Reference Example 3 was used, and “Betsukasite” was used.
Instead of 30 parts of ``1111-60T'', 18 parts of ``YS Polyster #2130'' [terpene manufactured by Yasushi Kogyo Co., Ltd.
A cured coating film was obtained by repeating the same operation as in Example 1, except that a phenolic resin was used, and the performance of this coating film was then evaluated. The results are summarized in Table 1. Comparative Example 1 Instead of resin (A-1), the same amount of resin (A'-
Example 1 except that it was changed to use 1)
A cured coating film for comparison was obtained in the same manner as above, and the performance of this coating film was then evaluated. The results are summarized in Table 1. Comparative Example 2 Abstaining from the use of “Betsukasite 1111-60T”, using resin (A-1) and “Albasite”
A cured coating film was obtained by repeating the same operation as in Example 1, except that the solid content weight ratio was changed to 90:10, and the performance was evaluated. The results are summarized in Table 1. Reference Example 5 [Example of preparation of graft copolymer (A)] “Hardren 14LLB” was replaced with “Hardren CPE-35” (chlorinated polyethylene manufactured by the same company;
Chlorinated polyethylene modified acrylic with a non-volatile content of 40.9% was prepared in the same manner as in Reference Example 1, except that 75 g of chlorination rate = 35%, non-volatile content = 20%) was used, and the amount of toluene used was changed to 55 g. Resin was obtained.
Hereinafter, this will be abbreviated as resin (A-4). Reference Example 6 [Example of preparation of graft copolymer (A)] Instead of "Hardren CPE-35", the same amount of "Hardren 14EV" (chlorinated ethylene-vinyl acetate copolymer made by the same company; chlorine ratio = 28%) A chlorinated ethylene-vinyl acetate copolymer-modified acrylic resin with a non-volatile content of 41% was obtained in the same manner as in Reference Example 5, except that the non-volatile content was changed to 41%. Hereinafter, this will be abbreviated as resin (A-5). Example 4 Same amount of resin (A-4) instead of resin (A-1)
except that 18 g of "Nippon Steel Macron V-120" (Macron-indene resin manufactured by Nippon Steel Chemical Industry Co., Ltd.) was used instead of "Betsukasite 1111-60T". A paint was prepared in the same manner as in Example 1, and then the performance of the paint film was evaluated.
The results are summarized in Table 1. Example 5 Same amount of resin (A-5) instead of resin (A-4)
A coating material was prepared in the same manner as in Example 4, except that the coating material was changed to use the following.Then, the coating film performance was evaluated. The results are summarized in Table 1. Comparative Example 3 A cured coating film for comparison was obtained in the same manner as in Example 1, except that "Hardren 14LLB" having the same solid content weight was used instead of "Betsukasite 1111-60T", and then this Performance evaluation of the coating film was performed. The results are summarized in Table 1. Comparative Example 4 A cured coating film for comparison was obtained in the same manner as in Example 1, except that a cyclized rubber having the same solid content was used instead of "Betsukasite 1111-60T", and then this coating film was We performed a performance evaluation on the following. The results are summarized in Table 1. In addition, in each of the above examples and comparative examples,
So-called clear paints, which do not use ``Alpaste 1109MA'' at all, were individually adjusted. The stability of each of the clear paints thus obtained was evaluated by visually determining the condition of each paint after storing it at room temperature for one month. The results are summarized in Table 1. 【table】

Claims (1)

[Claims] 1 (A) In the presence of chlorinated polyolefin having a chlorination rate of 50% by weight, 50 to 100 of (a-1) acrylic ester and/or methacrylic ester
and (a-2) 0 to 50% by weight of other vinyl monomers copolymerizable with the above (meth)acrylic acid esters (a-1) with the above chlorinated polyolefin. , the monomer (a-1) and (a-
2) and the solid content weight ratio is 10:90 to 90:10.
99 to 50 parts by weight of a graft copolymer obtained by polymerizing in a ratio of type, ketone type, ester type,
Natural resin-modified maleic acid resin, terpene polymer, or chroman resin that is soluble in an alcohol-based or chlorinated solvent or a combined solvent and is compatible with the above-mentioned graft copolymer (A). A resin composition for coating material having good adhesion to polyolefin materials, characterized in that it contains 1 to 50 parts by weight as an essential component.