JPS5953557A - Coating resin composition - Google Patents

Abstract

PURPOSE:To provide the titled novel composition for the primer for a polyolefin base, having excellent adhesivity and solvent resistance, and containing specific amounts of vinyl compolymer having dicyclopentenyl groups and ethylenic unsaturated bonds, a chlorinated polyolefin and a curing catalyst. CONSTITUTION:The objective composition can be prepared, e.g. by compounding (A) a vinyl copolymer composed of (i) 1-40wt% of a monomer having dicyclopentenyl group and ethylenic unsaturated bond in the molecule [ e.g. dicyclopentenyl (meth)acrylate] and (ii) 60-99wt% of other copolymerizable monomers with (B) a chlorinated polyolefin (preferably having a chlorination ratio of 10- 40%) at a weight ratio of (10-90):(90-10), and mixing the above mixture with (C) 0.01-1wt% (based on the component A) of a curing catalyst (e.g. cobalt naphthenate). USE:Paint for the top-coating of various molded articles, structural materials, and structures (applicable as one-coat paint), a biner for printing ink, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new resin composition for coatings useful as L7, and its object is to coat films, sheets, or sheets that have not been subjected to any of the various surface treatments to impart paintability. For molded products, Uta, so-called untreated polyolefin base materials, it is til! It is an object of the present invention to provide a resin composition having good adhesion and solvent resistance, which can be applied in a one-coat manner.

Paints made from IIC's alkyd, acrylic, and epoxy resins have almost no adhesion to various molded products made of crystalline polyolefins with low polarity, and therefore, it is difficult to paint these polyolefin materials. , as a bride, especially Akkujisoku Polypropi!
It has been proposed to use non-modified maleic anhydride or ethylene-propylene copolymer modified with maleic anhydride, but although these have good adhesion to such materials, -1. has poor interlayer adhesion, and when used as a clear paint, the coating film becomes cloudy; on the other hand, when applied as an enamel paint system containing pigments, the pigment dispersion is significantly affected. There was a problem that the paint was inferior and lacked stability.

In addition, a method is known in which chlorinated polyolefin itself is used as a brimer and an acrylic resin is applied as a top coat, but this method has poor interlayer adhesion with Tosopko I, solvent resistance, and long-term durable adhesion. The disadvantage is that it decreases.

Furthermore, it is known that the chlorinated polyolefin itself can be used by binding Tonopko-1, but ttt! The hardness, solvent resistance, and weather resistance of the film deteriorate significantly, making it impractical.

Provides long-term adhesion to polyolefin materials, maintains interlayer adhesion with top coats, and provides coatings with excellent solvent resistance, hardness, etc.
As a coating resin composition with improved performance, a resin composition consisting of a chlorinated polyolefin and an acrylic (co)W1 combination is effective. The composition formed includes In as follows. That is, the chlorination rate is 50
When the amount exceeds Coulometric % (hereinafter abbreviated as %), the compatibility between the chlorinated polyolefin and the acrylic (co)polymer improves, but the adhesion and solvent resistance of the formed l1fJ film decreases, making it difficult for practical use. It is difficult. On the other hand, in order to improve adhesion, the chlorination rate should be 50% or less, for example, 35%.
This is possible by using a chlorinated polyolefin with a concentration of about 1.9%, but it lacks compatibility with the acrylic (co)polymer, and the stability of the paint becomes extremely poor, making it difficult to use practically.

However, in view of the existence of the prior art as described above, the present inventors first attempted to improve the compatibility between chlorinated polyolefin and vinyl yarn (polymer), and at the same time, developed a polyolefin-based material. As a result of intensive research aimed at improving and tightening the adhesion to The present invention was completed based on the discovery that not only the adhesion to m! recording materials but also the gasoline resistance of the coating film were improved.

That is, the present invention provides (1) a vinylic acid polymer having both dicyclopentenyl and ethylenically unsaturated bonds in the molecule; (II) a chlorinated polyolefin;
II) A hard polyolefin containing M & Ni, and these vinyl copolymers (+) and Ifi-treated polyolefin (n)
A polyolefin material having a ratio of 10 to 90 parts by weight and 190 to 10 parts by weight is used to provide a coating resin composition with good adhesion to substrates.

Here, in order to obtain a vinyl copolymer having the above-mentioned dicyclopentenyl group and ethylenically unsaturated bond, a monomer having both of these sites (bonds) is essential, and d and monomers are and other copolymerizable vinyl monomers☆
First, a monomer having a dicyclopentenyl group and an ethylenically unsaturated f11 bond has an ethylenically unsaturated bond in the molecule that can be easily copolymerized with other vinyl monomers, and an oxygen Monomers that have another type of double bond that has reactivity with compounds such as dicyclopentenyl (meth)acrylate, dicyclopentenyloxy (meth)acrylate, etc. , dicyclopentenyl fumarate, dicyclopentenyl maleate, dicyclopentenyl itaconate, and the like.

Typical vinyl monomers that can be copolymerized with these monomers include methyl(meth)acrylate,
Ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethyl'\xyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate Like (
meth)acrylic acid ester; β-hyp 17xyethyl (meth)acrylate, β-hyp 1'roxyprovir (
Hydroxyl group-containing beaks such as meth)acrylate; acid group-containing monomers such as (meth)acrylic acid, fumaric acid, maleic acid, and itaconic acid; glycidyl-containing monomers such as glycidyl (meth)acrylate-1; Styrene, (meth)acrylonitrile, vinyl acetate, dibutyl fumarate, dimethylmale-1, dibutylitacone-1, (meth)acrylamide, N-methoxymethylacrylamide, etc. Vinyl monomers having functional groups such as , acid groups, or glycidyl groups may be used together without any problem, but copolymerization of such functional group-containing monomers may cause problems in the coating film. It is particularly recommended because it improves solvent resistance and pigment dispersibility.

The vinyl copolymer (1) contains 1 monomer having both a dicyclopentenyl group and an ethylenically unsaturated bond.
-40% by weight, and 60-99% by weight of other monomers copolymerizable with the monomer, which improves adhesion to polyolefin materials and substrates and improves coating film. In terms of gasoline resistance! It is lT'+'fA.

The vinyl copolymer (+) is one that is subjected to a known polymerization method, and is
As a polymerization initiator that emits 4.1i
Benzoyl 7cm - Makeup ID, A.)'Bisisobutyronitrile, 1. - Buti 71 horn < -: t 4' cybenenoate, di-t-butyl peroxide, etc. JTIL) - This? It can be easily obtained by 8-liquid polymerization and cooling.

Typical solvents to be used at this time are aromatic systems such as luene and xylene, and acid-c ・F.
t, it: a-, f esters such as CH/l/, meglue ketone, meglue isobug.

Walls containing ketone-based solvents such as ketones, these
It is also possible to use two or more types together.

The above-mentioned chlorinated polyolefin (It) and (yojll)
(A polyolefin with a coefficient of <50% or less, preferably 10 to 40%, is referred to as a polyolefin, and -C representative nζ) 6 ζ is ethylene, propylene, 1-butene, 3-methyl- Homopolymers or copolymers of α-molefin such as 1-butene-3-methyl-1-heptene, ethylene-vinyl acid, ethylene-butadiene, ethylene-acid ester, etc. There are copolymers of α-olefins and other vinyl-based m m (such as chlorinated polyethylene, chlorinated polyethylene, etc.). Examples include IJ propylene, chlorinated ethylene-propylene copolymer, or chlorinated ethylene-vinyl acetate polymer.

Regarding the chlorination rate of the chlorinated polyolefin, if the chlorination rate exceeds 50%, the adhesion to the polyolefin base material decreases, so the determination of the chlorination rate is based on the adhesion and flexibility. This should be done while considering various coating IQ performances such as hardness and hardness, preferably 10 to 10.
It should be 40%, even more preferably 15-35%, in this way a resin composition with the most balanced coating performance is obtained.

The blending ratio (solid weight parts ratio) of the vinyl copolymer (1) and the chlorinated polyolefin (n) is 9.
0:10-10:90, preferably 85:15-601
It is preferable that the value be within the range of 0.

By the way, since the vinyl copolymer (1) has a wrinkle free pentenyl group as a double bond that can react with oxygen etc. in the molecule, the curability of the copolymer (1) is improved. Therefore, it is preferable to use a curing catalyst, and by using such a curing catalyst, not only the curability but also the coating film performance are significantly improved.

Here, typical examples of the curing catalyst (III) include cobalt naphthenate, lead naphthenate, manganese naphthenate, etc., and the amount of the catalyst (T11) used is determined by the amount of the vinyl copolymer (+). 0 for the heavy dawn.
A culm degree of 0.01 to 1% is sufficient.

The composition of the present invention contains a vinyl copolymer N), a chlorinated polyolefin (It), and a curing agent &'J (III) as described in J2 below as essential components. It can be obtained by blending and squeezing by means.

The thus obtained composition of the present invention has excellent long-term adhesion and adhesion in a broad sense such as glabella adhesion with the top coat, as well as a cured film with excellent solvent resistance. It provides a coating film and can be widely applied to various polyolefin materials and base materials such as various molded products such as films and sheets. For example, it can be used as a primer in coating polyolefin molded products. It can also be used as a binder for printing inks, and can also be used as a binder for printing inks, especially for various molded products made from polyolefin. Useful for structures or constructions.

The composition of the present invention is a molded article or structure of a homopolymer or copolymer of ethylene, propylene, ]-butylene or 3-medylene-1-butylene. It can also be applied as a paint to structures, etc., and exhibits excellent adhesion to polyolefin molded products containing fillers such as titanium oxide, talc, and silica. It goes without saying that it may be used as an enamel paint, or in the form of a mixture of known and commonly used additive components such as pigments and leveling agents.

Next, the present invention will be specifically explained with reference to Reference Examples and Examples, where all parts and percentages are based on weight unless otherwise specified.

Reference Example 1 (Example of Preparation of Vinyl Copolymer (I)) 70 parts of toluene was charged into a reactor equipped with a stirrer and a cooler, the temperature inside the reactor was raised to 110°C, and 10 parts of dicyclopentenyl acrylate was added. part, methyl methacrylate 6
A monomer mixture consisting of 0 parts of azobisisobutyronitrile and 0.5 parts of t-butylperoxybenzoate in 30 parts of toluene was prepared. , was added dropwise over 4 hours.

Thereafter, the same temperature was maintained for 8 hours to obtain a vinyl copolymer solution with a nonvolatile content of 50.5%. Hereinafter, this will be abbreviated as vinyl copolymer (1-1).

Reference Example 2 (same as above) Same as Example 1, except that the composition of the Qtjtt mixture was 20 parts of dicyclopentenyl acrylate, 50 parts of methyl methacrylate, and 30 parts of isobutyl methacrylate, and the nonvolatile content was 50 parts. A solution of .3% vinyl copolymer was obtained. Reference Example 3 Using this as a vinyl copolymer (1-2), the composition of the monomer mixture was changed to
) I7-20 parts, 60 parts of methyl methacrylate, and 30 parts of isobutyl methacrylate (Reference Example 1)
A vinyl copolymer solution having a nonvolatile content of 50.4% was obtained by filtration in the same manner as above. This is a vinyl-based coelectric composite (I-3).
shall be.

Example 1 200 parts ε of the vinyl copolymer (1-1) of Reference Example 1, 1-bardrene+4LLI1. + (Toyo Kasei Kogyo ((15 chlorinated 1! Lipropylene; non-volatile content = 15%
, flattening rate -28%) 166.7 parts, 6! ! 4su゛7
Thenic acid: + Hull l-(04 parts and t”r/Rebase l-11-1l09) After blending 13.6 parts of aluminum base day made by Toyo Aluminum A Kiku, use thinner and Riki Iwata for 15 seconds with a knob. The desired paint was obtained by adjusting the viscosity.

Next, apply this paint to "Noblen l'1c-31'lJ".
After spray painting and tightening (Mitsubishi Yuka@Tori's Voliv D-Pyrene), a coating film was obtained by forced drying at 60°C for 30 minutes.

This coating has a metallic feel.
5. Adhesion to molded products (initial A (1st side))
is also good.

4- after 6 months? Due to the good results of the ripple mark test, the durability of the paint film is 1! It is also known that ゛ is maintained i].

In addition, this coating film had good solvent (gasoline) resistance and alkaline resistance, and a pencil hardness of F-H.

In addition, initial adhesion, drunk gasoline property, 1Ii11"Full 1
The elasticity and hardness ζ were each measured and evaluated at 411 days after vaginal formation (the same applies hereinafter).

Example 2 The same procedure as Example 1 was carried out except that the same amount of the vinyl copolymer (1-2) of Reference Example 2 was used instead of the vinyl copolymer (1-1). The material was made into a paint and a paint film performance test was conducted. The test results for Sowara are summarized in Table 1.

Example 3 A paint was produced in the same manner as in Example 1, except that the vinyl copolymer (1-3) of Reference Example 3 was used instead of Vinyl 7 (= co-T17 union (+-)). A coating film performance test was carried out.The test results are shown in Table 1 under the heading F.

Example 4 ``Verjiren 14LL [l, instead of 1, 33.3 parts [Superchron Old/IIIJ (Ryosumi Kokusaku Pulp 0
A coating was prepared in the same manner as in Example 1, except that chlorinated polypropylene made from Kiku (chlorinated polypropylene: -43%, non-volatile content -60%) was used. Ta. The test results are summarized in Table 1.

Claims (1)

[Claims] As essential components, it contains (1) a vinyl copolymer having a dicyclopentenyl group and an ethylenically unsaturated bond in the molecule, (1) a chlorinated polyolefin, and (III) a curing catalyst, and - the above vinyl copolymer (
1) and the above chlorinated polyolefin (II) are 10 to 9
A resin composition for paint, characterized in that the ratio is 0 parts by weight to 90 to 10 m rJ parts.