JPH11315252A - Coating resin composition, method for coating therewith, and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition having excellent weather resistance, oil resistance, reduced tendency to repel a Magic ink (R), stability of its duration, stability of peeling force, non-migration to a pressure-sensitive adhesive layer, heat resistance, and reduced sound of peeling, and a process for coating therewith, and a laminate prepared by using the resin composition. SOLUTION: There is provided the coating resin composition having a hydroxyl value of 50-130 mgKOH/g and prepared by copolymerizing a mixture prepared by mixing (A) a copolymer resin having active hydrogen atoms in the molecule and produced from a polydialkylsiloxane having a polymerizable unsaturated group, an organopolysilsesquioxane having a polymerizable unsaturated bond, and a compound having another polymerizable unsaturated bond, and, optically, another copolymer resin (C), and (B) a crosslinking agent reactive with an active hydrogen, desirably an isocyanate compound in an amount to give 0.5-1.5 times by equivalent of isocyanate groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a resin composition used as a coating material for various substrates. More specifically, a resin composition for a top coat used for the purpose of modifying the surface of various substrates, a resin composition used for a back surface treatment agent for an adhesive tape or an adhesive film, and furthermore weather resistance, oil resistance, Resin composition excellent in magic ink repellency and its sustained stability, stability of peeling force, non-migration to pressure-sensitive adhesive layer, heat resistance and low peeling sound, coating method of the resin composition and resin composition The present invention relates to a laminate using an object.

[0002]

2. Description of the Related Art As a material for imparting properties such as water repellency, oil resistance, magic ink repellency (hereinafter referred to as ink repellency) and releasability to various substrate surfaces by a coating method (coating method). Generally, fluorine-based compounds and fluororesins having low surface energy, silicone-based compounds and silicone resins are used. In particular, silicone-based compounds and silicone-based resins have attracted attention as environmentally friendly materials in recent years. Among them, silicone-based resins have been spotlighted from the viewpoints of non-silicone contamination, durability, and sustainability of performance.

[0003] Silicone resins used for this purpose include, for example, copolymerizing a monomer or oligomer containing silicon and having a radical polymerizable reactive group such as a vinyl group with another vinyl monomer. Further, it can be easily obtained by grafting the silicon-containing monomer or oligomer to various resins. Also,
As another method, a silicon-containing compound having a reactive group such as an epoxy group, an amino group, or a mercapto group is introduced into various resins by using various reactions. Can easily be obtained by mixing with

[0004] In recent years, as a silicone resin having not only the characteristics possessed by silicone but also a reforming effect and sustainability of the performance without impairing the inherent performance of the coating film, for example, JP-A-58-154766. , JP 5
JP-A-9-20360 and JP-A-59-126478 propose a coating composition comprising a copolymer of a radically polymerizable silicone macromonomer and another radically polymerizable monomer.

However, in the performance evaluation of coating films using these copolymers, the contact angle to water and stain resistance at the initial stage of coating, or 40 ° C. × 4 at 1% concentration of a commercially available detergent.
Although there is an effect on the contact angle with water in a test such as air drying overnight after immersion for a period of time, there is no specific description of the effect of sustainability. Further improvement, including that, is strongly demanded.

Further, as a copolymer of a radical polymerizable silicone macromonomer and another radical polymerizable monomer, for example, a highly weather-resistant paint proposed in JP-A-61-151272, furthermore, an active energy ray-reactive functional group Energy ray-curable silicone graft polymer obtained by copolymerizing a compound having
No.), an uncompounded silicone macromonomer is dispersed in a copolymer of 2 to 50% by weight of a silicone macromonomer as a graft component and a copolymerizable monomer forming a main chain having a glass transition point of 20 ° C. or higher. Release agent (JP-A-1-146983), a substrate for a plastic pressure-sensitive adhesive tape having a release layer made of a copolymer obtained by radical polymerization of a silicone macromonomer and a radical copolymerizable monomer (JP-A-8-302306) No.), a coating composition for preventing sticking paper and graffiti by copolymerizing a silicone macromonomer, several kinds of acrylic monomers and a monomer having a hydrolyzable silyl group such as γ-methacryloyloxypropyltrimethoxysilane No. 9-100455) and the like.

[0007] JP-A-61-151272 discloses that
A graft copolymer (G1) of a radical polymerizable compound (a) mainly composed of (meth) acrylate and a radical polymerizable silicone macromonomer (b), or (a),
A highly weather-resistant paint containing a graft copolymer (G2) of (b) and a crosslinkable monomer (c) as a main component has been proposed, but a coating film obtained from a resin containing G1 as a main component has a crosslinked structure. Since it does not exist, it is insufficient in not only mechanical strength but also chemical performance, and particularly lacks in long-term retention of physical and chemical performance. On the other hand, unlike the former, the coating film obtained from the resin containing G2 as a main component is cross-linked, and thus has a higher UV resistance (UVCON is used as an evaluation device in this report) and a higher resistance than the G1 system. Although the toluene property is greatly improved, the inventors of the present invention have applied a UV fluorescent lamp type test method (JIS D0205 method) to the G2 coating film.
According to the evaluation, the gloss retention of the coating film after irradiation for about 3,000 hours, which is said to be a measure of high weather resistance, is far from 80%. Furthermore, it is insufficient in terms of long-term durability such as water repellency, lubricity, mold release properties, and ink repellency.

Similarly, the silicone macromonomer copolymers disclosed in JP-A-61-19606, JP-A-1-146983, JP-A-8-302306, JP-A-9-100445 and the like are also active. In terms of long-term sustainability such as water-based properties, lubricity, releasability, and ink repellency, in particular, the durability of performance under outdoor exposure is insufficient, and it cannot be said that it is necessarily sufficient for outdoor use.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a weather-resistant, water-repellent, oil-resistant, magic ink repellent, lubricating, strippable, and durable, and more particularly, durable under outdoor exposure. An object of the present invention is to provide a coating resin composition which is excellent in heat resistance, has no migration of silicone to the adhesive layer (silicone migration property), and has excellent low peeling sound.

[0010]

Means for Solving the Problems The present inventors have high weather resistance, and are excellent in water repellency, oil resistance, ink repellency, lubricity, peelability, and their sustainability, especially in outdoor exposure. As a result of intensive studies to obtain a coating resin that has no silicone migration property and excellent low peeling sound, specific organopolysiloxane and silicone macromonomer are incorporated into the molecular skeleton and react with active hydrogen. It has been found that the above-mentioned object can be achieved by a coating resin composition containing a curing agent having two or more reactive groups in a molecule capable of forming a crosslinked structure.
The present invention has been completed.

That is, the present invention relates to [1] a polydialkylsiloxane (a1) having at least one polymerizable unsaturated group per molecule, an organopolysilsesquioxane (a2) having a polymerizable unsaturated group, and A copolymer resin (A) produced from another compound having a polymerizable unsaturated group (a3) and having two or more active hydrogens in a molecule;
A resin composition for coating, comprising: a crosslinking agent (B) having two or more reactive groups in a molecule capable of forming a crosslinked structure by reacting with active hydrogen; [2] at least one resin per molecule. The resin composition for coating according to the above item 1, wherein the polymerizable unsaturated group of the polydialkylsiloxane (a1) having two polymerizable unsaturated groups is a vinyl group or a substituted vinyl group, [3] a copolymer resin (A ), The component derived from (a1) is 0.5 to 60% by weight, the component derived from (a2) is 0.5 to 20% by weight, and the component derived from (a3) is 20 to 99% by weight.
0% by weight and has a hydroxyl value of 10 to 130.
(KOHmg / g), the resin composition for coating according to the above 1 or 2,

[4] The compound (a3) having another polymerizable unsaturated group contains (meth) acrylic acid, and its content in the copolymer resin (A) is 0.5 to 5.0% by weight. The above 1 which is
The resin composition for coating according to any one of claims 1 to 3,
[5] The coating resin composition according to any one of [1] to [4], wherein the number average molecular weight of the polydialkylsiloxane (a1) having at least one polymerizable unsaturated group per molecule is from 500 to 50,000. Object, [6] above 1
The copolymer resin (A) according to any one of (1) to (5),
9% by weight, a composition containing 98 to 1% by weight of another copolymer resin (C), and two or more reactive groups capable of forming a crosslinked structure by reacting with active hydrogen in the molecule. A resin composition for coating, comprising: a crosslinking agent (B);

[7] The copolymer resin (C) is an organopolysilsesquioxane (c1) having a polymerizable unsaturated group.
And (8) a copolymer resin (C) which is produced from the compound (c2) having a polymerizable unsaturated group, and a component derived from (c1). 0.5 to 20% by weight, and the component derived from (c2)
The resin composition for coating according to the above 7, which is contained in the range of 9 to 99.5% by weight, [9] the copolymer resin (C) having a hydroxyl value of 10 to 130 (KOH mg / g). 8. The coating resin composition according to any one of [8] to [10], wherein the reactive group of the crosslinking agent (B) having two or more reactive groups in a molecule capable of forming a crosslinked structure by reacting with active hydrogen is isocyanate or The coating resin composition according to any one of the above 1 to 9, which is any of melamine or a combination thereof,

[11] A crosslinking agent (B) having two or more reactive groups in a molecule capable of forming a crosslinked structure by reacting with active hydrogen.
Is the isocyanate compound, [12] the isocyanate compound is a urethane-modified isocyanate monomer, an allophanate-modified product, an isocyanurate-modified product, a buret-modified product, a carbodiimide-modified product, or a block. The above 11 which is at least one selected from modified isocyanates
[13] A resin composition for preventing graffiti or sticking paper, wherein the resin composition for coating according to any one of the above 1 to 12 is used as a top coat agent, [14] ] 1 to 1 above
2. The resin composition for a back surface treating agent, wherein the resin composition for coating according to any one of 2) is used as a back surface treating agent for an adhesive tape or a film.

[15] The component derived from (a1) is 0.5 to 1
5% by weight, a component derived from (a2) in a range of 0.5 to 20% by weight and (meth) acrylic acid in a range of 0.5 to 5.0% by weight, and a hydroxyl value of 50 to 130 (KOH mg / g)
15. A copolymer resin (A), and a cross-linking agent (B) blended so that the isocyanate group is 0.5 to 1.5 times equivalent to the hydroxyl group. [16] The above-mentioned 1 to 15
The coating resin composition according to any one of, paper,
Coating to a thickness of 0.02 to 150 g / m ^{2 on} at least one surface of a substrate selected from processed paper, cloth, plastic products, plastic films, metals, porcelain tiles, concretes, wood products, or these coated products. [17] The coating method according to any one of [1] to [15], wherein the coating resin composition according to any one of [1] to [15] is applied to at least one surface of the substrate to a thickness of 0.05 to 10 g / m ^2. 16. The coating method according to item 16, [18] the laminate obtained by the coating method according to item 16 or 17, and [19] the layered product according to item 18 is a protective film for surface protection. It is a laminate characterized by the above.

Hereinafter, the present invention will be described in detail. In this specification, “(meth) acryl” means both “methacryl” and “acryl”, and “(meth) acrylate” means both “methacrylate” and “acrylate”. The copolymer resin (A) produced from the polydialkylsiloxane having a polymerizable unsaturated group, the organopolysilsesquioxane having a polymerizable unsaturated group, and another compound having a polymerizable unsaturated group according to the present invention. Has two or more active hydrogens that can react with the crosslinking agent (B) to form a crosslinked structure. Examples of the substituent having an active hydrogen include a hydroxyl group, a mercapto group, an amino group, a carboxyl group, and the like, and a hydroxyl group is particularly preferable in consideration of reactivity with the crosslinking agent (B), stability, and the like.

In the copolymer resin (A) of the present invention, the polyorganosilsesquioxane (a2) having a polymerizable unsaturated group used for copolymerization is reported by Nakahama et al.
eprints Japan, 29 (1), p.73 (1980)]
No. 281616, JP-A-4-28722, JP-A-6-286
As known in, for example, 287307, those obtained by hydrolyzing / co-condensing trialkoxysilane having a polymerizable unsaturated group such as vinyl group or (meth) acryl group and alkyltrialkoxysilane described below, for example. The main structure is preferably an oligomer having a polymerizable unsaturated group and an alkyl group in a side chain, and having a number average molecular weight of several hundreds to several 10,000 in which the main skeleton of the molecule has a ladder shape. .

Examples of the trialkoxysilane having a polymerizable unsaturated group such as a vinyl group and a (meth) acryl group include vinyltrimethoxysilane, vinyltriethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ -(Meth) acryloyloxypropyltriethoxysilane and the like. Further, a trihalosilane can be used instead of the trialkoxysilane. Examples of the trihalosilane include vinyltrichlorosilane and γ- (meth) acryloyloxypropyltrichlorosilane.

Examples of the alkyltrialkoxysilane to be hydrolyzed and co-condensed with these silane compounds include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane and the like. May be used instead of alkyltrihalosilane, such as methyltrichlorosilane, ethyltrichlorosilane, etc .; Compounds are also exemplified. One or more of these silane compounds and alkylsilane compounds having a polymerizable unsaturated group can be used.

The organopolysilsesquioxane (a2) having a polymerizable unsaturated group used in the copolymer resin (A) of the present invention is a functional organopolysilsesquioxane described in JP-A-8-73593. Like the sun, the main chain terminal is sealed with a silylating agent. The amount of the organopolysilsesquioxane having a polymerizable unsaturated group to be used is preferably 0.5 to 20% by weight, more preferably 1.0 to 15% by weight, based on the weight of the copolymer resin (A). If the amount of the organopolysilsesquioxane having a polymerizable unsaturated group used is less than 0.5% by weight, the heat resistance and the stain resistance of the resin are insufficient, while the amount used is 20% by weight. If it exceeds, gelation tends to occur during polymerization, and the pot life of a coating resin composition containing a predetermined amount of a curing agent is significantly reduced, which is not economically preferable.

The polymerizable unsaturated group in the organopolysilsesquioxane having a polymerizable unsaturated group (for example,
The content of the (meth) acryloxy group) is preferably about 5 to 60 mol%, more preferably 8 to 50 mol% of all side chains of the organopolysilsesquioxane having the polymerizable unsaturated group.
Mol%, particularly preferably 8 to 40 mol%. When the content of the polymerizable unsaturated group is less than 5 mol%, the curability of the coating resin composition containing a predetermined amount of the crosslinking agent is insufficient, and when the content exceeds 60 mol%, the polymerization during the polymerization is stopped. In addition, the gelation tends to occur easily, and the raw material price increases, which is not economically preferable.

Next, the polydialkylsiloxane (a1) having a polymerizable unsaturated group used for the copolymer resin (A) of the present invention has a (meth) acrylate type polymerizable unsaturated group at the terminal of the molecular chain. Straight-chain silicone oligomers such as those described in JP-A-58-154766 and JP-A-59-154766.
Silicone macromonomers described in JP-A-126478, JP-A-59-20360, JP-A-61-151272 and the like can be used in the present invention.

The polydialkylsiloxane having a polymerizable unsaturated group has a number average molecular weight of 500 to 5
It is 0,000. When the number average molecular weight is less than 500, the ink is not sufficiently stable in terms of sustainability of ink repellency and low peeling sound. When the number average molecular weight exceeds 50,000, the compatibility with the resin and the The coating (coating) property is lacking, and particularly when the coating is performed at a thickness of less than about 1 g / m ² , the thickness may become uneven, which is not preferable. The amount of the polydialkylsiloxane having a polymerizable unsaturated group is preferably 0.5 to 60% by weight. 0.5 used
If the amount is less than 60% by weight, not only the sustainability of the ink repelling and the peeling force are insufficient, but also the sound of low peeling sound becomes insufficient. In particular, not only lacking in thin film coating properties, but also insufficient compatibility with the later-described copolymer resin (C) and other resin (a3) preferably used in the resin composition of the present invention, and It is not preferable because it becomes difficult to obtain a coating film.

The hydroxyl value of the copolymer resin (A) of the present invention is preferably from 10 to 130 KOH mg / g, more preferably from 20 to 120 KOH mg / g per gram of the resin.
It is. If the hydroxyl value is less than 10 KOHmg / g, the curability will be insufficient and sufficient low releasability will not be obtained.
If it exceeds 30 KOH mg / g, the resin composition for coating obtained by blending a predetermined amount of a crosslinking agent becomes hard and brittle, which is not preferable.

As a method for imparting a hydroxyl group for maintaining the hydroxyl value of the copolymer resin (A) in the above range, a commonly used method of copolymerizing a polymerizable unsaturated compound containing a hydroxyl group is used. Adopted.

Examples of the polymerizable unsaturated compound having a hydroxyl group include allyl alcohol, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) ) A hydroxyl group-containing polymerizable unsaturated compound such as hydroxybutyl acrylate or 2-hydroxybutyl (meth) acrylate, or a hydroxyl group-containing (meth) acryl monomer, and ε
-Adducts with lactones such as caprolactone (for example,
Daicel Chemical Co., Ltd .; trade name "Placcel FA-1"
"Placcel FA-2", "Placcel FA-3",
"Placcel FM-1", "Placcel FM-2",
"Placcel FM-3").

The polymerizable unsaturated compound other than the above-mentioned hydroxyl group-containing polymerizable unsaturated compound used in the production of the copolymer resin (A) of the present invention is not particularly limited and copolymerizes relatively easily. Any compound may be used. That is, such a compound is a polymerizable unsaturated compound substituted with a linear or branched or cyclic saturated or unsaturated hydrocarbon having 1 to about 20 carbon atoms, for example,
(Meth) acrylic acid, maleic anhydride, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate,
Butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, ethylene, propylene, butylene-1, ethyl vinyl ether, isobutyl vinyl ether, Butyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate,
Examples include vinyl caproate, vinyl pivalate, (meth) acrylonitrile, styrene, vinyl toluene, α-methylstyrene, (meth) acrylamide, dimethylaminoethyl (meth) acrylate, and the like.

In the resin composition of the present invention, the above-mentioned resin (A) can be used alone as a resin. It is preferable to blend the copolymer resin (C). The copolymer resin (C) is a compound obtained by polymerizing a general polymerizable unsaturated compound such as (meth) acrylic acid and the ester compound by a known method, and the copolymer resin (C) is also a copolymer resin. Like the polymer resin (A), it is preferable to react with the crosslinking agent (B) to form a crosslinked structure. That is, the copolymer (C) is also preferably a resin having the above-mentioned active hydrogen, and particularly preferably a resin having a hydroxyl group.

The polymerizable unsaturated compound used in the production of the copolymer resin (C) of the present invention is not particularly limited, and may be any compound that can be relatively easily copolymerized.
That is, such a compound is a polymerizable unsaturated compound substituted with a linear, branched, or cyclic saturated or unsaturated hydrocarbon having 1 to about 20 carbon atoms, such as (meth) acrylic. Acid, maleic anhydride, methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, Ethylene, propylene, butylene-1, ethyl vinyl ether, isobutyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl pivalate,
(Meth) acrylonitrile, styrene, vinyltoluene, α-methylstyrene, (meth) acrylamide, dimethylaminoethyl (meth) acrylate, and the like.

The method for imparting a hydroxyl group to the copolymer resin (C) is similar to the method for imparting a hydroxyl group to the polymer resin (A), in which a commonly used hydroxyl group-containing polymerizable unsaturated compound is copolymerized. A polymerization method is employed. The hydroxyl value of the copolymer resin (C) is preferably 10 to 130K.
OHmg / g, more preferably 20 to 120 KOHmg
/ G. If the hydroxyl value is less than 10 KOH mg / g, the curability becomes insufficient, and it takes a considerable time to form a coating film, which may hinder work efficiency.
If the amount exceeds g / g, the resin composition for coating obtained by blending a predetermined amount of a crosslinking agent becomes hard and brittle, which is not preferable.

Examples of the hydroxyl group-containing polymerizable unsaturated compound include, for example, allyl alcohol, (meth) acrylic acid 2-
Hydroxyethyl, hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Hydroxy group-containing polymerizable unsaturated compounds such as hydroxybutyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate, and adducts of hydroxyl group-containing (meth) acrylic monomers with lactones such as ε-caprolactone (for example, “ (Placcel FA-1), "Placcel FA-2", "Placcel FA-3", "Placcel FM-1", "Placcel FM-2", "Placcel FM-3" or more (trade name of Daicel Chemical Co., Ltd.) No.

The copolymer resin (C) of the present invention comprises an organopolysilsesquioxane (c) having a polymerizable unsaturated group.
Copolymer resins produced from 1) and other compounds having polymerizable unsaturated groups (c2) are particularly preferred. In this case, the organopolysilsesquioxane (c1) having a polymerizable unsaturated group used for copolymerization is an oligomer similar to the component (a2) for producing the above-mentioned copolymer resin (A) of the present invention. The amount of the organopolysilsesquioxane (c1) having a polymerizable unsaturated group is preferably 0.5 to 20% by weight, more preferably 1.0 to 20% by weight, based on the weight of the copolymer resin (C). %. If the amount of the organopolysilsesquioxane having a polymerizable unsaturated group is less than 0.5% by weight, the heat resistance, stainability and the like of the resin are insufficient.
On the other hand, if the used amount exceeds 20% by weight, gelation tends to occur during polymerization, and the pot life of the resin composition for coating formed by mixing a predetermined amount of a curing agent is significantly lacking.
Further, it is not economically preferable.

The production of the copolymer resin (A) and the copolymer resin (C) used in the present invention is described in, for example, Paint Technology Handbook (edited by Japan Paint Technology Association, published in 1987, Nikkan Kogyo Shimbun, p. 154). ) Can be carried out by a known method. In the copolymer resin (A), an organopolysilsesquioxane having a polymerizable unsaturated group (a2), a polydialkylsiloxane having a polymerizable unsaturated group (a1), a hydroxyl group-containing polymerizable unsaturated compound and It is preferable to obtain the compound (a3) appropriately selected from the group of polymerizable unsaturated compounds other than those mentioned above by radical copolymerization in an organic solvent.

In the copolymer resin (C), a compound appropriately selected from the group consisting of a hydroxyl group-containing polymerizable unsaturated compound and the above-mentioned polymerizable unsaturated compounds, preferably a polymerizable unsaturated group The compounds selected from the group consisting of organopolysilsesquioxane (c1), a hydroxyl-containing polymerizable unsaturated compound and the other polymerizable unsaturated compounds (c2) listed above are radically copolymerized in an organic solvent. It is preferred to obtain by.

The number average molecular weight of the copolymer resin (A) and copolymer resin (C) of the present invention thus obtained is not particularly limited, but is preferably about 2,000 to 200,000, more preferably 5,000-50,000.

The copolymer (A) and the copolymer (C) produced by radical polymerization in an organic solvent as described above.
Is obtained as a resin solution of the used organic solvent, but may be used as it is in the reaction with the crosslinking agent (B) to be added next, or the resin solution may be further diluted with an organic solvent and used. Is also good.

Next, the component (B) used in the present invention, which is a crosslinkable reactive group of a crosslinking agent having two or more reactive groups in a molecule capable of forming a crosslinked structure by reacting with active hydrogen, includes: Are exemplified. An epoxy group, an isocyanate group, a methylolmelamine group, an oxazoline group, an acylcarbamate group, a β-hydroxycarbamate group, a methylolated amino group, an acetal group, an aminoglycolate ether group, an acetoacetoxy group, or an acid anhydride group. Of these, an isocyanate group and a methylolmelamine group are particularly preferred. As the component (B), two or more compounds may be used.

The compound containing an isocyanate group as the component (B) is a modified isocyanate monomer known in the art, such as a modified urethane, a modified allophanate,
It is selected from modified isocyanurate, modified buret, modified carbodiimide, and modified isocyanate.

The modified isocyanate monomer is obtained by modifying the isocyanate monomer described below for the purpose of improving undesired physical properties such as toxicity and controlling the reaction rate. The urethane-modified product is obtained by modifying an isocyanate monomer (or diisocyanate) with a shortage of polyol. The modified allophanate is formed by adding an isocyanate group to a urethane group. The modified isocyanurate has an isocyanurate ring in the molecule, and tends to have improved heat resistance. The modified buret is a compound in which an isocyanate group is added to a urea bond, and is a compound from which free isocyanate has been removed. In the modified carbodiimide, a carbodiimide bond is generated from a 2 mol isocyanate group by a decarboxylation gas reaction. When isocyanate is further added, uretonimine is formed, and carbodiimide and urethaneimine coexist in equilibrium. Blocked isocyanates can be obtained by reacting various blocking agents to temporarily mask the activity of isocyanate groups. Examples of the blocking agent include phenol-based blocking agents such as phenol and xylenol, and active hydrogen compounds such as oximes, lactams, and alcohols.

As the isocyanate monomer forming the modified product, tolylene diisocyanate (TDI), 4,4
4'-diphenylmethane diisocyanate (MDI),
Xylylene diisocyanate (XDI), naphthylene diisocyanate (NDI), paraphenylene diisocyanate (PPDI), tetramethyl xylylene diisocyanate (TMXDI), hexamethylene diisocyanate (HMDI), dicyclohexylmethane diisocyanate (CHMDI), isophorone diisocyanate (IPDI), Lysine diisocyanate (LDI), isopropylidene bis (4-cyclohexyl isocyanate) (IPC), hydrogenated xylylene diisocyanate (hydrogenated XDI), cyclohexyl diisocyanate (CHD)
I) and tolidine diisocyanate (TODI). The isocyanate monomer used in the present invention is not limited thereto, and is described in detail in, for example, "Synthesis, blending, functionalization and application development of latest polyurethane" (Technical Information Association, 1989). Have been.

Specific examples of the modified structure include the following trimethylolpropane (TMP) adduct (2a), biuret (2b), and isocyanurate (2c).

Embedded image

Embedded image

Embedded image (In the formula, R is an aliphatic hydrocarbon having 1 to 20 carbon atoms, an aromatic hydrocarbon, or an alicyclic hydrocarbon.)

For example, in xylene diisocyanate and hydrogenated xylylene diisocyanate, only the (2a) isomer
In isophorone diisocyanate, (2a) and (2a)
c) is known. The above structure is a model structure,
For example, biuret of hexamethylene diisocyanate is generally shown as a trimer, but there are also trimers or more multimers, and there are those mainly containing trimers and those mainly containing pentamers, and both are used. be able to.

Examples of the polyisocyanate used in the present invention include blocked isocyanates blocked with phenols such as phenol and xylenol, oximes, lactams and alcohols, using the above-mentioned diisocyanates and modified products thereof as blocking agents. Can be. The amount of the polyisocyanate used in the present invention is 0.5 to 1.5 times equivalent of the amount of the hydroxyl group of the copolymer (A). When the amount of the isocyanate group is less than 0.5 equivalent, the curability of the formed film is insufficient, and the performance as the back surface treatment agent layer cannot be sufficiently obtained. Not only is it impossible to further improve the coating film performance, but the presence of an excessive amount of polyisocyanate reduces water resistance and moisture resistance, and is not economically preferable.

In order to further promote the curability of the coating resin composition of the present invention, if necessary, for example, inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid and salts thereof, formic acid, acetic acid, oxalic acid, maleic acid, Organic acids such as phthalic acid, benzoic acid and paratoluenesulfonic acid and derivatives thereof, di-n-butyltin diacetate, di-n-butyltin dioctate, di-
Organotin compounds such as n-butyltin dilaurate; organic zirconium compounds such as tetrabutylzirconate and butoxytris (acetylacetonato) zirconium; amine compounds such as ethylenediamine, diethylenetriamine, metaphenylenediamine, diethanolamine and triethanolamine; Organic aluminum compounds such as acetylacetonato) aluminum and tris (ethylacetonato) aluminum can be used. Further, if necessary, known antioxidants, light stabilizers, heat stabilizers, coloring agents, flame retardants, fillers, plasticizers, and the like may be added as long as the desired performance is not lost.

The coating resin composition of the present invention is required for the copolymer resin (A) or the composition comprising the copolymer resin (A) and the copolymer resin (C) and a predetermined amount of the crosslinking agent (B). It can be manufactured by a well-known method generally used by parties in the coating and coating industries, etc. by adding an organic solvent according to the method.

Useful organic solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as methyl acetate, ethyl acetate, butyl acetate and cellosolve acetate; and aromatic hydrocarbons such as toluene and xylene. And ethers such as tetrahydrofuran and dioxane; and alcohols such as methanol, ethanol isopropyl alcohol, butanol, ethylene glycol and propylene glycol. In general, the organic solvents are often used in a mixture of two or more.

The coating resin composition of the present invention thus diluted to an appropriate solid content is coated on various substrates by the coating method described above. For the purpose of preventing graffiti or sticking paper, for example, as a top coat agent, it is used as a top coat agent on the walls of building structures, telephone poles made of concrete or the like, benches such as parks, public toilets, underpasses and tunnels.
It is applied with a thickness of 00 g / m ² . On the other hand, for the purpose of the back surface treatment agent, for example, cellophane, soft PVC film,
Polyolefin film and various laminated films,
About 0.0 on the surface opposite to the adhesive treatment layer such as cloth or processed paper
The coating is applied at a thickness of ^{2 to 2} g / m ² .

The thus-obtained coating resin composition of the present invention for preventing graffiti or sticking paper, and for treating a back surface treatment agent, comprises:
It is used in the coating method / apparatus generally adopted in this industry. Usually, for the purpose of preventing graffiti or sticking paper, a method of manually applying the resin solution of the coating resin composition using a brush or a roller, a spray coating method, a roll coater method, and the like are employed. Then, usually, after applying the back surface treatment liquid to a substrate using a gravure, a Meyer bar coater, a roll coater, or the like, a curing treatment is performed by heating. As a method of the heat treatment, a method generally employed in the art,
For example, a method using a heat oven, an infrared heater, or the like can be applied. Generally, 50 to 200 ° C., particularly 80 to 150 ° C. is employed. In addition, if necessary, after heating and curing, for example, 40 to 200 ° C.
So-called aging can be performed in a temperature atmosphere of about 60 ° C. for several hours to several days.

[0049]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Production Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples. In addition, each physical property value in an Example and a comparative example was measured according to the following method.

(1) Stability over time of treating agent A resin composition was prepared using a mixed solvent of butyl acetate / xylene / Solfit AC so that the solid content concentration became 5.0% by weight. The time change was examined, and the time at which the viscosity became twice the initial value was determined. The solution viscosity was measured using a B-type viscometer, rotor No. 1 and rotation speed 60.
It was measured at rpm.

(2) Peel Strength A predetermined amount of the resin composition is applied to the surface of a stainless steel substrate, and the resin composition is heated in a hot air dryer at a predetermined temperature to form a cured film. Width 18
mm) with a constant weight and bonded at 23 ° C. for 24 hours. Next, one end of the cellophane tape was pulled at a peeling angle of 180 ° and a peeling speed of 0.5 mm / min using a tensile tester, and the force required for peeling was measured. .

(3) Weather resistance A coating resin composition having a solid content adjusted to 30% by weight was applied to a urethane coating surface of an aluminum substrate previously coated with a commercially available white urethane coating, after being cured by a spray method. The coating was applied so that the film thickness became 25 to 30 μm, and dried and cured to form a cured coating film. JIS for this coated substrate
3,000 according to the UV fluorescent lamp test method of D0205 method
The gloss retention (%) after time irradiation was measured.

(4) Ink repellency and its sustained stability A predetermined amount of the coating resin composition is applied to the surface of a stainless steel substrate and heated with a hot air drier at a predetermined temperature to form a cured film (about 20 to 25 μm). Oil-based magic ink (Zebra, Mackey) 5 colors (red, blue, black,
(Yellow, green), and a reeding property of each ink when a 30 mm straight line was drawn with a thick line having a thickness of about 5 mm was visually observed. At this time, if the repelling is fine dot-like, "repelling ◎", if the repelling is slightly large dot-like, "repelling ○", if some repelling remains but a thick line appears, "repelling △", repelling If it was not drawn and was drawn in a line, it was judged as "repelling property x".

(5) Residual Adhesion Rate A commercially available cellophane tape (width 18 mm) was adhered to the cured film prepared in the same manner as described above under a constant load to adjust the condition, and the tape was peeled off from the cured film. It was again attached to a stainless steel substrate and left at 23 ° C. for 24 hours.
The tape was then peeled at a 180 ° peel angle of 0.5 mm /
The film was pulled at a speed of one minute, and the force required for the peeling was measured, and this was defined as the adhesive strength A (g / 18 mm). In addition, the same cellophane tape was pasted on the same stainless steel substrate in advance, and the adhesive strength B (g / 18 mm) when left and pulled under the same conditions and method as above was measured, and the residual adhesive ratio (%) was calculated according to the following equation. .

## EQU1 ## Residual adhesion rate (%) = {(adhesive strength A) / (adhesive strength B)} × 100

(6) Silicone transferability The surface of the cured film prepared in the same manner as above
After covering the cardboard with a load of 10 kg / cm ² and adjusting the condition at 50% RH and 23 ° C. for 24 hours, the propylene film is Peel off and draw a thick line with a width of 6 mm with a length of about 3 cm using oil-based ink (manufactured by Zebra, Mackey) black on the surface in contact with the cured film, and visually observe the “repellence” of the ink. If no repelling was observed, no silicone migration was found. Conversely, if repelling was found, silicone migration was judged to be present.

(7) Peeling Sound A commercially available cellophane tape (18 mm wide) and a vinyl tape having a length of 10 cm were adhered to a surface-finished aluminum substrate, and peeled at a peeling angle of about 90 ° and a peeling speed of 12 m / min. The level of the peeling noise generated when
Rank (very low) and C rank (very high), and the middle was determined as B rank (medium). Next, using a resin composition of the present invention or a comparative example, after adjusting with a mixed solvent of ethyl acetate / acetone so that the solid content concentration becomes 5% by weight, the thickness of the coating film of this resin solution was measured using a Meyer bar. A cured film is formed on the urethane surface of a commercially available white urethane undercoated aluminum substrate so as to have a thickness of about 5 μm, dried at 120 ° C. for 3 minutes, and then aged at 50 ° C. for 2 days to form a test specimen. The cellophane tape used above was similarly adhered at a length of about 10 cm, and the peeling sound when peeling off under the same conditions was examined to determine the level.

Production Example 1 Production of Organopolysilsesquioxane (a2-1) Having a Polymerizable Unsaturated Group A 300-ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with γ-. 24.84 g of methacryloyloxypropyl trimethoxysilane (100 m
mol), 160.48 g of methyltriethoxysilane
(900 mmol) and 54.06 g of pure water (3,000 m
mol), and the solution temperature was maintained at 5 ° C. while stirring under a nitrogen stream. Then, 10.13 g of a 3.6% by weight aqueous hydrochloric acid solution was added dropwise over 30 minutes.
It was kept at 0 ° C. for 60 minutes. Next, the solution was heated to 70 ° C. and reacted for 180 minutes, and then 24.9 g (153.35 mmol) of hexamethylsiloxane was added to carry out a silylation reaction at 70 ° C. for 180 minutes. The obtained reaction solution was cooled to 40 ° C., and 13.2 g of a 4.25% by weight aqueous solution of potassium hydroxide was added to neutralize the system.
Let stand for hours. The lower layer portion of the liquid separated into two layers was collected, 100 g of butyl acetate was added to the lower layer liquid, and the mixture was concentrated under stirring at 40 ° C. under a reduced pressure of 200 mmHg.
After distilling off g of the liquid, 350 g of butyl acetate was further added at room temperature, followed by stirring for 60 minutes. The obtained solution was filtered through a 0.8 μ filter to obtain a colorless and transparent solution 44.
0 g was obtained. The number average molecular weight of the organopolysilsesquioxane having a polymerizable unsaturated group measured by GPC (gel permeation chromatography) was 3,500. As a result of GPC analysis, no peak derived from the raw material silane monomer was detected, and thus it was considered that there was no unreacted monomer in the obtained organopolysilsesquioxane having a polymerizable unsaturated group. In addition, ¹ H
From the analysis of-, ¹³ C- and ²⁹ Si-NMR spectra, the molar ratio of the γ-methacryloyloxypropyl group and methyl group in the side chain was equal to the molar ratio of the charged silane monomer, and was 1: 9.
Met. This organopolysilsesquioxane having a polymerizable unsaturated group is hereinafter referred to as polymer a2-1.

Production Example 2: Production of organopolysilsesquioxane (a2-2) having a polymerizable unsaturated group Using the same apparatus as in Production Example 1, 74.51 g of γ-methacryloyloxypropyltrimethoxysilane ( 300
mmol), 124.82 g of methyltriethoxysilane
The number average molecular weight measured by GPC of the organopolysilsesquioxane having a polymerizable unsaturated group produced under the same conditions as in Production Example 1 except for (700 mmol) was 2,500. As a result of GPC analysis, no peak derived from the raw material silane monomer was detected, and thus it was considered that there was no unreacted monomer in the obtained organopolysilsesquioxane having a polymerizable unsaturated group. The ¹ H-,
^From the analysis of ¹³ C- and ²⁹ Si-NMR spectra, the molar ratio of the γ-methacryloyloxypropyl group and the methyl group in the side chain was equal to the molar ratio of the charged silane monomer, and was 3: 7. This organopolysilsesquioxane having a polymerizable unsaturated group is hereinafter abbreviated as polymer a2-2.

Production Example 3: Production of organopolysilsesquioxane (a2-3) having a polymerizable unsaturated group Using the same apparatus as in Production Example 1, 22.35 g of γ-methacryloyloxypropyltrimethoxysilane ( 90m
mol), 160.48 g of methyltriethoxysilane
(900 mmol), phenyltrimethoxysilane 1.
Except for 98 g (10 mmol), the number average molecular weight measured by GPC of the organopolysilsesquioxane having a polymerizable unsaturated group produced under the same conditions as in Production Example 1 was 3,000.
It was 0. As a result of GPC analysis, no peak derived from the raw material silane monomer was detected, and thus it was considered that there was no unreacted monomer in the obtained organopolysilsesquioxane having a polymerizable unsaturated group. Also ¹
From the analysis of the H-, ¹³ C- and ²⁹ Si-NMR spectra, the molar ratio of the side chain γ-methacryloyloxypropyl group, methyl group and phenyl group was equal to the molar ratio of the charged silane monomer and was 9: 90: 1. . This organopolysilsesquioxane having a polymerizable unsaturated group is hereinafter referred to as polymer a2-3.

Production Example 4 Production of Copolymer Resin A1 The following composition was placed in a 1-liter (L) flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and placed in a nitrogen stream at 90 ° C. After reacting for 6 hours at
The reaction rate by PC was 99%, and the number average molecular weight was 12,12.
000, a copolymer A1 having a weight average molecular weight of 28,500 was obtained. The hydroxyl value is 51.7 KOHmg / g.

Polymer (a2-1) 15 parts by weight AK-32 (silicone macromonomer manufactured by Toagosei Co., Ltd.) 15 parts by weight Methyl methacrylate 19 parts by weight n-butyl methacrylate 25 parts by weight Hydroxyethyl methacrylate 24 parts by weight Parts acrylic acid 1 part by weight azobisisobutyronitrile 1 part by weight butyl acetate 100 parts by weight

Production Example 5 Production of Copolymer Resin A2 The following composition was placed in a 1 L flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and reacted at 90 ° C. for 6 hours in a nitrogen stream. As a result, the conversion by GPC was 99%, and a copolymer A2 having a number average molecular weight of 11,600 and a weight average molecular weight of 37,000 was obtained. The hydroxyl value is 17.3 KOHmg / g.

Polymer (a2-2) 5 parts by weight AK-15 (silicone macromonomer manufactured by Toagosei Co., Ltd.) 50 parts by weight Methyl methacrylate 12.5 parts by weight n-butyl methacrylate 23 parts by weight Hydroxyethyl methacrylate 8 parts by weight Acrylic acid 0.5 parts by weight Azobisisobutyronitrile 1 part by weight 100 parts by weight of butyl acetate

Production Example 6: Production of copolymer resin A3 The following composition was placed in a 1 L flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and reacted at 90 ° C. for 6 hours in a nitrogen stream. As a result, the conversion by GPC was 99%, and a copolymer A3 having a number average molecular weight of 12,100 and a weight average molecular weight of 30,400 was obtained. The hydroxyl value is 30.2 KOHmg / g.

Polymer (a2-3) 9 parts by weight AK-30 (silicon macromonomer manufactured by Toagosei Co., Ltd.) 30 parts by weight Methyl methacrylate 16 parts by weight n-butyl methacrylate 29 parts by weight Hydroxyethyl methacrylate 14 parts by weight Parts acrylic acid 1 part by weight azobisisobutyronitrile 1 part by weight butyl acetate 100 parts by weight

Production Example 7 Production of Copolymer Resin A4 The following composition was placed in a 1 L flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and reacted at 90 ° C. for 6 hours in a nitrogen stream. As a result, the conversion by GPC was 99%, and a copolymer A4 having a number average molecular weight of 10,200 and a weight average molecular weight of 27,100 was obtained. The hydroxyl value is 30.2 KOHmg / g.

AK-30 (silicon macromonomer manufactured by Toagosei Co., Ltd.) 30 parts by weight Methyl methacrylate 19 parts by weight n-butyl methacrylate 35 parts by weight Hydroxyethyl methacrylate 14 parts by weight Acrylic acid 1 part by weight Azobisiso Butyronitrile 1 part by weight 100 parts by weight of butyl acetate

Production Example 8: Production of Copolymer Resin C1 The following composition was placed in a 1 L flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and reacted at 90 ° C. for 6 hours in a nitrogen stream. As a result, the conversion by GPC was 99%, and a copolymer C1 having a number average molecular weight of 11,400 and a weight average molecular weight of 35,500 was obtained. The hydroxyl value is 53.9 KOHmg / g.

Methyl methacrylate 35 parts by weight n-butyl methacrylate 38 parts by weight Hydroxyethyl methacrylate 25 parts by weight Acrylic acid 1 part by weight Azobisisobutyronitrile 1 part by weight 100 parts by weight butyl acetate

Production Example 9 Production of Copolymer Resin C2 The following composition was placed in a 1 L flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and reacted at 90 ° C. for 6 hours in a nitrogen stream. As a result, the conversion by GPC was 99%, and a copolymer C2 having a number average molecular weight of 10,600 and a weight average molecular weight of 28,000 was obtained. The hydroxyl value is 52.8 KOHmg / g.

Methyl methacrylate 23 parts by weight N-butyl methacrylate 43 parts by weight Hydroxyethyl methacrylate 24.5 parts by weight 2-ethylhexyl acrylate 7 parts by weight Acrylic acid 1.5 parts by weight Azobisisobutyronitrile 1 part by weight 100 parts by weight of butyl acetate

Production Example 10 Production of Copolymer Resin C3 The following composition was placed in a 1 L flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and reacted at 90 ° C. for 6 hours in a nitrogen stream. As a result, the conversion by GPC was 99%, and a copolymer C3 having a number average molecular weight of 9,700 and a weight average molecular weight of 22,900 was obtained. The hydroxyl value is 2.4 KOHmg / g.

Methyl methacrylate 34 parts by weight n-butyl methacrylate 43 parts by weight Hydroxyethyl methacrylate 1.1 parts by weight 2-ethylhexyl acrylate 19.4 parts by weight Acrylic acid 1.5 parts by weight Azobisisobutyronitrile 1 Parts by weight butyl acetate 100 parts by weight

Production Example 11 Production of Copolymer Resin C4 The following composition was placed in a 1 L flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and reacted at 90 ° C. for 6 hours in a nitrogen stream. As a result, the conversion by GPC was 99%, and a copolymer C4 having a number average molecular weight of 11,400 and a weight average molecular weight of 35,500 was obtained. The hydroxyl value is 45.3 KOHmg / g.

Polymer (a2-3) 7 parts by weight Methyl methacrylate 16 parts by weight n-butyl methacrylate 41 parts by weight Hydroxyethyl methacrylate 21 parts by weight 12.3 parts by weight of 2-ethylhexyl acrylate 1.7 parts by weight of acrylic acid Azobisisobutyronitrile 1 part by weight butyl acetate 100 parts by weight

Production Example 12 Production of Copolymer Resin C5 The following composition was placed in a 1 L flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and reacted at 90 ° C. for 6 hours in a nitrogen stream. As a result, the conversion by GPC was 99%, and a copolymer C5 having a number average molecular weight of 10,600 and a weight average molecular weight of 28,000 was obtained. The hydroxyl value is 25.2 KOHmg / g.

Polymer (a2-2) 3 parts by weight Methyl methacrylate 20 parts by weight n-butyl methacrylate 39 parts by weight Hydroxyethyl methacrylate 11.7 parts by weight 2-ethylhexyl acrylate 24 parts by weight Acrylic acid 1.3 parts by weight Azobisisobutyronitrile 1 part by weight butyl acetate 100 parts by weight

Production Example 13 Production of Copolymer Resin C6 The following composition was placed in a 1 L flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and reacted at 90 ° C. for 6 hours in a nitrogen stream. As a result, the conversion by GPC was 99%, and a copolymer C6 having a number average molecular weight of 16,700 and a weight average molecular weight of 89,000 was obtained. The hydroxyl value is 24.6 KOHmg / g.

Polymer (a2-2) 30 parts by weight Methyl methacrylate 16 parts by weight N-butyl methacrylate 27 parts by weight Hydroxyethyl methacrylate 11.4 parts by weight 2-ethylhexyl acrylate 11 parts by weight Acrylic acid 3.6 parts by weight Azobisisobutyronitrile 1 part by weight butyl acetate 100 parts by weight

Production Example 14: Synthesis of polydialkylsiloxane having a vinyl substituent (a1-1) Modification of carbinol having a molecular weight of 3,400 in a 200 mL flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. Polydimethylsiloxane (KF600
2, Shin-Etsu Chemical Co., Ltd.) (120 g) and then 139 mg of dibutyltin dilaurate were introduced and mixed and stirred at 15 ° C. Next, after slowly dropping 9.0 g of 2-isocyanateethyl methacrylate over 20 minutes,
The reaction temperature was raised to 40 ° C., and the reaction was further performed for 90 minutes. This was cooled to room temperature to obtain 127 g of a silicone macromonomer having a vinyl substituent.
This is designated as polymer a1-1.

Production Example 15 Synthesis of Polymerization-Reactive Organopolysilsesquioxane (a2-4) A 1-L flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with γ-methacryloyloxypropyltrimethoxy. 50.45 g of silane (203 mmo
l), 398.41 g of methyltriethoxysilane (2.2
34 mmol), phenyltrimethoxysilane 12.3
9 g (63 mmol) and 135.19 g of pure water (7.5
00 mmol), and the solution temperature was maintained at 5 ° C. while stirring under a nitrogen stream. Next, 25 g of a 3.6% by weight aqueous hydrochloric acid solution was added dropwise over 30 minutes, then the solution temperature was raised to 10 ° C. and maintained for 60 minutes, and the reaction temperature was raised to 70 ° C. to carry out a reaction for 180 minutes. Then, 62.04 g (382 mmol) of hexamethyldisiloxane was added thereto, and the mixture was further stirred at 70 ° C. for 180 minutes. The solution temperature was lowered to 40 ° C., and a 4.25% by weight aqueous solution of potassium hydroxide was added. 33 g was added, and the mixture was allowed to stand at room temperature for 12 hours. The lower layer portion of the liquid separated from the two layers was extracted, 250 g of butyl acetate was added to the remaining upper layer liquid, and the mixture was stirred at 40 ° C. and 200 mmH.
After concentrating under a reduced pressure of g to distill out 250 g of the liquid, 960 g of butyl acetate was further added at room temperature, followed by stirring for 60 minutes. After filtering the obtained solution, a butyl acetate solution of a polymerization reactive organopolysilsesquioxane having a weight average molecular weight (Mw) of 9,000 and a number average molecular weight (Mn) of 3,500 as measured by GPC. 1,200g
Obtained. As a result of the GPC analysis, no peak derived from the raw material silane monomer was detected, and it was considered that no unreacted monomer remained in the obtained polymerizable organopolysilsesquioxane. Also, ¹ H-, ¹³ C- and
^From the analysis of the ²⁹ Si-NMR spectrum, the molar ratio of the side chain γ-methacryloyloxypropyl group, methyl group and phenyl group was almost equal to the molar ratio of the corresponding silane monomer charged, and was 3: 36: 1. This polymerizable organopolysilsesquioxane is hereinafter abbreviated as polymer a2-4.

Production Example 16: Synthesis of polymerization-reactive organopolysilsesquioxane (a2-5) A 1-L flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with γ-methacryloyloxypropyltrimethoxy. 121.07 g of silane (975 mmo
1), 86.93 g of methyltriethoxysilane (975)
mmol), 4.96 g of phenyltrimethoxysilane
(50 mmol) and 54.06 g of pure water (6,000 m
mol), and the solution temperature was maintained at 5 ° C. while stirring under a nitrogen stream. Next, 10 g of a 3.6% by weight aqueous hydrochloric acid solution was added dropwise over 30 minutes, and the solution temperature was reduced to 10 ° C.
, And the temperature of the solution was raised to 70 ° C. for 18 minutes.
A 0 minute reaction was performed. Then, 13.89 g (171 mmol) of hexamethyldisiloxane was added thereto, and the mixture was further stirred at 70 ° C. for 180 minutes.
℃ to 4.25% by weight aqueous solution of potassium hydroxide
3 g was added, and the mixture was allowed to stand at room temperature for 12 hours. The lower layer portion of the liquid separated into two layers was extracted, 150 g of butyl acetate was added to the remaining upper layer solution, and the mixture was concentrated at 40 ° C. under reduced pressure of 200 mmHg under stirring to distill 150 g of the liquid, and then cooled to room temperature. Further, 560 g of butyl acetate was added, and the mixture was stirred for 60 minutes. After filtering the obtained solution, a butyl acetate solution of a polymerization reactive organopolysilsesquioxane having a weight average molecular weight (Mw) of 3,200 and a number average molecular weight (Mn) of 2,000 as measured by GPC. Was obtained 700 g. As a result of the GPC analysis, no peak derived from the raw material silane monomer was detected, and it was considered that no unreacted monomer remained in the obtained polymerizable organopolysilsesquioxane. In addition, ¹ H-, ¹³ C- and ²⁹ Si-
From the analysis of the NMR spectrum, the molar ratio of the side chain γ-methacryloyloxypropyl group, methyl group and phenyl group is almost equal to the molar ratio of the corresponding silane monomer charged,
39: 39: 2. This polymerizable organopolysilsesquioxane is hereinafter abbreviated as polymer a2-5.

Production Example 17 Synthesis of Acrylic Copolymer (Copolymer A5) 1.8 g of polymer (a1) was placed in a 500 mL flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser.
-1), 27.0 g of polymer (a2-5), 32.54
g of 2-hydroxyethyl methacrylate, 37.55
g of methyl methacrylate, 71.10 g of n-butyl methacrylate, 23.04 g of 2-ethylhexyl acrylate, 5.4 g of acrylic acid, and 3.2 g of dodecyl mercaptan as a molecular weight regulator were introduced under a nitrogen stream at room temperature. The mixture was stirred for a minute to prepare a mixed monomer.
Then, butyl acetate 13 was added to a 500 mL flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser tube.
After 7.8 g of the mixture was stirred at room temperature for 30 minutes under a nitrogen stream, the temperature was raised to 80 ° C. 19.7 g of a 10% by weight butyl acetate solution
Was added dropwise over 180 minutes. Further, 3.3 g of the same initiator solution was added, and the reaction was carried out at 90 ° C. for 180 minutes. After the completion of the reaction, the reaction solution was cooled to room temperature and 360 g
A viscous liquid of a colorless and transparent acrylic copolymer (copolymer A5) was obtained. The weight average molecular weight by GPC is 42,000.
0 and the OH number is 77.9 KOH mg / g.

Production Example 18: Synthesis of acrylic copolymer (copolymer A6) 10.08 g of polymer (a1-1), 90.71 g of polymer (a2-4), 56.94 g of 2-hydroxyethyl Methacrylate, 25.03 g methyl methacrylate, 62.21 g n-butyl methacrylate, 23.
Using 04 g of 2-ethylhexyl acrylate, 2.3 g of acrylic acid and 3.9 g of dodecyl mercaptan, a mixed monomer was prepared in the same manner as in the copolymer A5. Then, 97.1 g of butyl acetate, mixed monomer 27
4.1 g of a 10% by weight butyl acetate solution of the same polymerization initiator 3
A copolymerization reaction was carried out under the same conditions as in Production Example 17 except that the amount was 0.4 g and the additional initiator was changed to 5.1 g.
0 g of a colorless transparent viscous liquid was obtained. The weight average molecular weight by GPC was 55,000, and the OH value was 121.8K.
OH mg / g. This acrylic copolymer will be described below.
Abbreviated as copolymer A6.

Production Example 19: Synthesis of Acrylic Copolymer (Copolymer A7) 19.36 g of methacryl-modified polydimethyl at one end was placed in a 300 mL flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. Siloxane (X-22-174D, manufactured by Shin-Etsu Chemical Co., Ltd.) (a1-2), 29.
81 g of polymer (a2-4), 34.16 g of 2-hydroxyethyl methacrylate, 36.29 g of methyl methacrylate, 71.10 g of n-butyl methacrylate, 23.0 g of 2-ethylhexyl acrylate,
6.8 g of acrylic acid and 2.0 g of dodecyl mercaptan as a molecular weight regulator were introduced, and the mixture was cooled to room temperature under nitrogen atmosphere at room temperature.
The mixture was stirred for 0 minutes to prepare a mixed monomer. Next, 153.9 g of butyl acetate was placed in a 500 mL flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, stirred at room temperature for 30 minutes under a nitrogen stream, and then heated to 80 ° C. To this, 222.6 g of the mixed monomer prepared above and 20.0 g of a 10% by weight butyl acetate solution of dimethyl 2,2'-azobisisobutyrate as a polymerization initiator were added dropwise over 180 minutes. Further, 3.3 g of the same initiator solution was added, and the reaction was carried out at 90 ° C. for 180 minutes. After the completion of the reaction, the reaction solution was cooled to room temperature to obtain 400 g of a colorless transparent viscous liquid (copolymer A7). G of the obtained copolymer A7
The weight average molecular weight by PC is 22,000 and OH
The value is 74.1 KOH mg / g.

Production Example 20 Synthesis of Acrylic Copolymer (Copolymer A8) 0.2 g of polymer (a1-
1), 49.65 g of polymer (a2-4), 35.79
g of 2-hydroxyethyl methacrylate, 35.04
g of methyl methacrylate, 71.10 g of n-butyl methacrylate, 23.04 g of 19.8 g of acrylic acid and 3.7 of dodecyl mercaptan as molecular weight regulator.
g was introduced and stirred at room temperature for 30 minutes under a nitrogen stream to prepare a mixed monomer. Then, into a 500 mL flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser,
After adding 135.1 g of butyl acetate and stirring at room temperature for 30 minutes in a nitrogen stream, the temperature was raised to 80 ° C., and 238.3 g of the mixed monomer prepared above and 2,2
22.6 g of a 10% by weight butyl acetate solution of dimethyl 2'-azobisisobutyrate was added dropwise over 180 minutes. Further, 3.8 g of the same initiator solution was added thereto, and the mixture was added at 90 ° C.
A 0 minute reaction was performed. After the completion of the reaction, the reaction solution was cooled to room temperature, and 400 g of an acrylic copolymer (Copolymer A)
8) A colorless transparent viscous liquid was obtained. The weight average molecular weight of the obtained copolymer A8 by GPC was 75,000,
The H value is 77.7 KOH mg / g.

Production Example 21: Synthesis of Acrylic Copolymer (Copolymer A9) 5.2 g of polymer (a1
-1), 0.9 g of polymer (a2-4), 56.94 g
2-hydroxyethyl methacrylate, 25.03 g
Of methyl methacrylate, 62.21 g of n-butyl methacrylate, 23.04 g of 2-ethylhexyl acrylate, and 0.23 g of acrylic acid, and 1.3 g of dodecyl mercaptan as a molecular weight regulator. Created. Then, 500 mL equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser tube
The flask was charged with 153.9 g of butyl acetate, stirred at room temperature for 30 minutes in a nitrogen stream, heated to 80 ° C., and mixed with 174.8 g of the mixed monomer previously prepared and 2,2 as a polymerization initiator. 18.6 g of a 10% by weight solution of dimethyl '-azobisisobutyrate in butyl acetate was added dropwise over 180 minutes. Then, 3.1 g of the same initiator solution was further added, and 90 ° C.
For 180 minutes. After the completion of the reaction, the reaction solution was cooled to room temperature to obtain 350 g of a colorless and transparent viscous liquid of an acrylic copolymer (copolymer A9). The weight average molecular weight of the obtained copolymer A9 by GPC is 18,000, and the OH value is 141 KOHmg / g.

Example 1 The copolymer resin A1 (resin concentration 50% by weight) produced by the above method was diluted with a mixed solvent of ethyl acetate / xylene = 1/1 so that the resin concentration was 30% by weight. After that, the polyisocyanate (Sumijur N, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was added so that the isocyanate group was 1.1 times the hydroxyl group in the resin solution.
-3500) and uniformly stirred to obtain a coating resin composition of the present invention. Using this coating resin composition, weather resistance, oil-based ink repellency and its persistence, residual adhesiveness, silicone transferability, and peeling sound were evaluated. Table 1 shows the results.

Example 2 A resin composition for coating of the present invention was prepared in the same manner as in Example 1 except that the copolymer resin A2 (resin concentration 50% by weight) produced by the above method was used. Table 1 shows the results of evaluation of weather resistance, ink repellency and its persistence, residual adhesiveness, silicone transferability, and peeling sound using this coating resin composition in the same manner as in Example 1.

Example 3 A coating resin composition of the present invention was prepared in the same manner as in Example 1 except that the copolymer resin A3 (resin concentration: 50% by weight) produced by the above method was used. Table 1 similarly shows the evaluation of weather resistance, ink repellency and its persistence, residual adhesiveness, silicone transferability, and peeling sound using this coating resin composition.

Example 4: 35% by weight of A3 (resin concentration: 50% by weight) produced by the above method and 65% by weight of (meth) acrylic copolymer resin C1 (resin concentration: 50% by weight) produced by the above method Is diluted with a mixed solvent of ethyl acetate / xylene = 1/1 so that the resin concentration becomes 30% by weight, and the isocyanate group is 0.8 to the hydroxyl group in the resin composition solution. A polyisocyanate (Sumijur N-3500, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was blended so as to be twice the amount, and uniformly stirred to obtain a coating resin composition of the present invention. Table 1 shows the results of evaluation of weather resistance, ink repellency and its persistence, residual adhesiveness, silicone transferability, and peeling sound using the resin composition for coating.

Example 5: A resin composition consisting of copolymer resin A3 (5% by weight) and copolymer resin C2 (95% by weight) was mixed in the same manner as in Example 4 by mixing ethyl acetate / xylene = 1/1. After diluting with a solvent so that the resin concentration becomes 30% by weight, polyisocyanate (Sumitomo Bayer Urethane Co., Ltd.) is used so that the isocyanate group becomes 1.0 times the hydroxyl group in the resin composition solution. Sumidure N-350
0) was blended and uniformly stirred to obtain a coating resin composition of the present invention. Table 1 similarly shows the results of evaluation of weather resistance, ink repellency and its persistence, residual adhesiveness, silicone transferability, and peeling sound using this coating resin composition.

Example 6: Similar to Example 4, copolymer resin A3 (15% by weight) and copolymer resin C2 (85% by weight)
Is diluted with a mixed solvent of ethyl acetate / xylene = 1/1 so that the resin concentration becomes 30% by weight, and then the isocyanate group is 1.0 to the hydroxyl group in the resin composition solution. Polyisocyanate (Sumijur N-3 manufactured by Sumitomo Bayer Urethane Co., Ltd.)
500) and uniformly stirred to obtain a coating resin composition of the present invention. Table 1 similarly shows the results of evaluation of weather resistance, ink repellency and its persistence, residual adhesiveness, silicone transferability, and peeling sound using this coating resin composition.

Example 7: Similar to Example 4, copolymer resin A3 (30% by weight) and copolymer resin C2 (70% by weight)
Is diluted with a mixed solvent of ethyl acetate / xylene = 1/1 so that the resin concentration becomes 30% by weight, and then the isocyanate group is 1.0 to the hydroxyl group in the resin composition solution. Polyisocyanate (Sumijur N-3 manufactured by Sumitomo Bayer Urethane Co., Ltd.)
500) and uniformly stirred to obtain a coating resin composition of the present invention. Table 1 similarly shows the results of evaluation of weather resistance, ink repellency and its persistence, residual adhesiveness, silicone transferability, and peeling sound using this coating resin composition.

Example 8: Similar to Example 4, copolymer resin A3 (45% by weight) and copolymer resin C2 (65% by weight)
Is diluted with a mixed solvent of ethyl acetate / xylene = 1/1 so that the resin concentration becomes 30% by weight, and then the isocyanate group is 1.0 to the hydroxyl group in the resin composition solution. Polyisocyanate (Sumijur N-3 manufactured by Sumitomo Bayer Urethane Co., Ltd.)
500) and uniformly stirred to obtain a coating resin composition of the present invention. Table 1 similarly shows the results of evaluation of weather resistance, ink repellency and its persistence, residual adhesiveness, silicone transferability, and peeling sound using this coating resin composition.

Example 9: 5% by weight of copolymer resin A3 (resin concentration: 50% by weight) produced by the above method and copolymer resin C5 (resin concentration: 50% by weight) produced by the above method 9
Ethyl acetate / xylene =
After diluting with a 1/1 mixed solvent so that the resin concentration becomes 30% by weight, the polyisocyanate (Sumitomo Bayer) is used so that the isocyanate group becomes 1.0 times the hydroxyl group in the resin composition solution. (Sumidur N-3500 manufactured by Urethane Co., Ltd.) was blended and uniformly stirred to obtain a coating resin composition of the present invention. Table 1 similarly shows the results of evaluation of weather resistance, ink repellency and its persistence, residual adhesiveness, silicone transferability, and peeling sound using this coating resin composition.

Example 10: A resin composition comprising copolymer resin A3 (15% by weight) and copolymer resin C5 (85% by weight) was prepared in the same manner as in Example 9 by using ethyl acetate / xylene = 1 /
After diluting with a mixed solvent of Example 1 so that the resin concentration becomes 30% by weight, the polyisocyanate (Sumitomo Bayer Urethane (Sumitomo Bayer Urethane (TM)) is used so that the isocyanate group becomes 1.0 times the hydroxyl group in the resin composition solution. Sumijur N-
3500) and uniformly stirred to obtain a coating resin composition of the present invention. Table 1 similarly shows the results of evaluation of weather resistance, ink repellency and its persistence, residual adhesiveness, silicone transferability, and peeling sound using this coating resin composition.

Example 11: A resin composition comprising copolymer resin A3 (30% by weight) and copolymer resin C5 (70% by weight) was prepared in the same manner as in Example 9 by using ethyl acetate / xylene = 1 /
After diluting with a mixed solvent of Example 1 so that the resin concentration becomes 30% by weight, the polyisocyanate (Sumitomo Bayer Urethane (Sumitomo Bayer Urethane (TM)) is used so that the isocyanate group becomes 1.0 times the hydroxyl group in the resin composition solution. Sumijur N-
3500) and uniformly stirred to obtain a coating resin composition of the present invention. Table 1 similarly shows the results of evaluation of weather resistance, ink repellency and its persistence, residual adhesiveness, silicone transferability, and peeling sound using this coating resin composition.

Example 12: A resin composition comprising copolymer resin A3 (45% by weight) and copolymer resin C5 (55% by weight) was prepared in the same manner as in Example 9 by using ethyl acetate / xylene = 1 /
After diluting with a mixed solvent of Example 1 so that the resin concentration becomes 30% by weight, the polyisocyanate (Sumitomo Bayer Urethane (Sumitomo Bayer Urethane (TM)) is used so that the isocyanate group becomes 1.0 times the hydroxyl group in the resin composition solution. Sumijur N-
3500) and uniformly stirred to obtain a coating resin composition of the present invention. Table 1 similarly shows the results of evaluation of weather resistance, ink repellency and its persistence, residual adhesiveness, silicone transferability, and peeling sound using this coating resin composition.

Example 13: Copolymer resin A1 (resin concentration 50% by weight) produced by the above method was diluted with a mixed solvent of ethyl acetate / xylene = 1/1 so that the resin concentration was 30% by weight. After that, a polyisocyanate (Sumidur N-3200 manufactured by Sumitomo Bayer Urethane Co., Ltd.) was blended so that the isocyanate group was 1.2 times the amount of the hydroxyl group in the resin solution, and the mixture was uniformly stirred. A resin composition for coating of the present invention was obtained. Table 1 similarly shows the results of evaluation of weather resistance, ink repellency and its persistence, residual adhesiveness, silicone transferability, and peeling sound using this coating resin composition.

Example 14: Copolymer resin A1 (resin concentration 50% by weight) produced by the above method was diluted with a mixed solvent of ethyl acetate / xylene = 1/1 so that the resin concentration was 30% by weight. After that, polyisocyanate (Sumitomo Bayer Urethane Co., Ltd.'s Sumidur L-1375) was blended so that the isocyanate group was 1.2 times the amount of the hydroxyl group in the resin solution, and the mixture was stirred uniformly. A resin composition for coating of the present invention was obtained. Table 1 similarly shows the results of evaluation of weather resistance, ink repellency and its persistence, residual adhesiveness, silicone transferability, and peeling sound using this coating resin composition.

Comparative Example 1: Copolymer resin A4 (resin concentration: 50% by weight) produced by the above method was diluted with a mixed solvent of ethyl acetate / xylene = 1/1 so that the resin concentration became 30% by weight. After that, the polyisocyanate (Sumijur N, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was added so that the isocyanate groups became 1.1 times the hydroxyl groups in the resin solution.
-3500) and uniformly stirred to obtain a resin composition for coating. Table 1 similarly shows the results of evaluation of weather resistance, ink repellency and its persistence, residual adhesiveness, silicone transferability, and peeling sound using this coating resin composition.

Comparative Example 2 A copolymer resin C1 (resin concentration 50% by weight) was used in place of the copolymer resin A1.
A coating resin composition was prepared in the same manner as in Example 1, and using this coating resin composition, weather resistance, ink repellency and its persistence, residual adhesion, silicone transferability, and peeling sound were evaluated. The results are shown in Table 1 as in Example 1.

Comparative Example 3: 50% by weight of copolymer resin A4 (resin concentration: 50% by weight) produced by the above method and C4 (resin concentration: 50% by weight) produced by the above method
After diluting a resin composition consisting of 50% by weight with a mixed solvent of ethyl acetate / xylene = 1/1 so that the resin concentration becomes 30% by weight, isocyanate groups are converted to hydroxyl groups in the resin composition solution. A polyisocyanate (Sumidur N-3500, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was blended in a 1.1-fold amount, and the mixture was stirred uniformly to obtain a coating resin composition. Table 1 similarly shows the results of evaluation of weather resistance, ink repellency and its persistence, residual adhesiveness, silicone transferability, and peeling sound using this coating resin composition.

[0105]

[Table 1]

As shown in Table 1, the resin compositions for coating of the present invention (Examples 1 to 14) are extremely low in terms of weather resistance, ink repellency and its persistence, residual adhesiveness, silicone transferability and peeling sound. It is clear that it is an excellent and very useful material. On the other hand, when a copolymer (A1) containing neither the component (a1) nor the component (a2) is used (Comparative Example 2), other physical properties which are excellent in the residual adhesion ratio are not good. Is enough. When the copolymer (A) containing no component (a2) was used as the copolymer (A) (Comparative Example 1), it was excellent in the initial ink repellency and the peeling sound,
Poor weather resistance, durability of ink repellency, residual adhesiveness, and migration to silicone. The component (a) is used as the copolymer (A).
In the case where the copolymer containing the component (a2) was mixed with the copolymer containing no 2) (Comparative Example 3), the weather resistance and the residual adhesion ratio were slightly improved, but they were still insufficient, and conversely, the ink repellency was poor. Is less persistent.

Example 15: Ethyl acetate / xylene = 1 /
A resin composition for coating was prepared in the same manner as in Example 5 so that the solid content concentration of the resin was 30% by weight using the mixed solvent of No. 1, and an ivory-colored urethane paint was preliminarily applied and dried and cured. It was top-coated with a coating thickness of 100 g / m ² and dried and cured at room temperature for one week. An attempt was made to paste a paper advertisement with a commercially available cellophane tape or gum tape on the obtained coating film, but not only was it difficult to paste, but also characters and pictures could be drawn with commercially available thick magic ink. could not.

Example 16: The resin composition for coating of Example 7 was further diluted with a mixed solution of ethyl acetate / acetone = 1/1 so that the solid content of the resin was 2% by weight. Using a No. 6 Meyer bar, the solution was coated with an acrylic pressure-sensitive adhesive layer on one side so that the coating thickness became 1 μm. After heat treatment at 120 ° C. for 1 minute, condition control at 50 ° C. for 24 hours was performed to prepare an adhesive film. A commercially available cellophane tape was stuck to the rear surface of the film, and a 180 ° peel angle and a 0.5 ° peel angle were applied.
When the cellophane tape was peeled at a pulling speed of mm / min, the peel resistance (peel strength) was 5 to 10 g / 18.
mm. Furthermore, the residual adhesion rate of the adhesive film is 100
%, There was no migration of silicone, and the peeling sound was ◎.

Example 17: Copolymer resin A5 as an acrylic copolymer, hexamethylene diisocyanate isocyanurate type polyisocyanate (Sumitomo Bayer Urethane Co., Ltd., Sumidur N-3500) as an isocyanate compound, and a diluting solvent 49.4 parts by weight, 5.3 parts by weight, and 45.3 parts by weight of propylene glycol methyl ether acetate were uniformly mixed using a paint shaker to obtain a composition. Table 2 shows the results of evaluating the aging stability, the peel strength, the residual adhesion rate, and the silicone transferability using this composition.

Example 18: Copolymer resin A5 as an acrylic copolymer, hexamethylene diisocyanate isocyanurate type polyisocyanate (Sumitomo Bayer Urethane Co., Ltd., Sumidur N-3500) as an isocyanate compound, and a diluting solvent 47.3 parts by weight, 6.3 parts by weight, and 46.3 parts by weight of propylene glycol methyl ether acetate were uniformly mixed using a paint shaker to obtain a composition. Table 2 shows the results of evaluating the aging stability, the peel strength, the residual adhesion rate, and the silicone transferability using this composition.

Example 19: 42.1 parts by weight of copolymer resin A6 as an acrylic copolymer, 42.1 parts by weight of propylene glycol methyl ether acetate as an isocyanate compound, and 8.9 parts by weight of propylene glycol methyl ether acetate as a diluent solvent , 48.9 parts by weight were uniformly mixed using a paint shaker to obtain a desired composition. Table 2 shows the results of evaluating the aging stability, the peel strength, the residual adhesion rate, and the silicone transferability using this composition.

Example 20: Copolymer resin A7 as an acrylic copolymer, Sumidur N-3500 as an isocyanate compound, and propylene glycol methyl ether acetate as a diluent were 47.7 parts by weight and 6.1 parts by weight, respectively. , 46.1 parts by weight, and uniformly mixed using a paint shaker to obtain a desired composition. Table 2 shows the results of evaluating various performances in the same manner.

Example 21: Copolymer resin A8 as an acrylic copolymer, hexamethylene diisocyanate biuret-type polyisocyanate as an isocyanate compound (Sumijur N, manufactured by Sumitomo Bayer Urethane Co., Ltd.)
-3200), 47.9 parts by weight of propylene glycol methyl ether acetate as a diluent, 6.0 parts by weight.
Parts by weight, 46.0 parts by weight, were weighed and uniformly mixed using a paint shaker to obtain a desired composition. Table 2 shows the results of evaluating various performances in the same manner.

Example 22: Copolymer resin A5 as an acrylic copolymer, TDI-based TMP adduct type polyisocyanate (Sumitomo Bayer Urethane Co., Ltd., Sumidur L-1375) as an isocyanate compound, and propylene glycol as a diluent 45.2 parts by weight, 9.9 parts by weight, and 44.9 parts by weight of methyl ether acetate were weighed and uniformly mixed using a paint shaker to obtain a desired composition. Table 2 shows the results of evaluating various performances in the same manner.

[0115]

[Table 2]

As shown in Table 2, the resin composition of the present invention has not only a moderate peel strength, an excellent residual adhesiveness and non-migratory property of silicone, but also a very excellent stability over time after preparation as a back treatment liquid. Therefore, the work efficiency is improved, and the generation of lossy products is suppressed as much as possible, so that an extremely economical material is provided.

Example 23: The composition obtained in Example 17 was further diluted with a mixed solvent of ethyl acetate / acetone / toluene so that the solid content of the resin became 2.0%. Using a Meyer bar coater,
A polyester film having a thickness of 50 μm has a thickness of 0.5 g /
After coating so as to obtain m ² , heat treatment was performed through a hot-air oven at 150 ° C. to obtain a laminated structure. When the peel strength of the laminated film was measured, it was 97 g / 18 mm, the residual adhesive ratio was 92%, and no migration of silicone was observed.

Example 24: The composition obtained in Example 20 was further diluted with a mixed solvent of ethyl acetate / acetone / toluene so that the solid content of the resin became 5.0%. Using a Meyer bar coater,
2.5 g on 80 μm thick polyethylene laminated paper
/ M ² , and then heat-treated through a 130 ° C. hot air oven to obtain a laminated structure. When the peel strength of the laminated film was measured, it was 80 g / 18 mm, the residual adhesive ratio was 95%, and no migration of silicone was observed.

[0119]

The resin composition for coating according to the present invention comprises:
At present, it aims to protect landscapes, such as graffiti and stickers, which have become social issues, and has excellent weather resistance, magic and other ink repellency and its sustainability. It is very useful as a topcoat composition for surface protection of various structures and articles that require
When used as a back surface treatment agent for tapes, films, adhesive cloths, adhesive labels, protective films, etc.), it is extremely useful in terms of excellent residual adhesion, non-silicone transferability, and low peeling sound. .

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C08F 290/06 C08F 290/06 C09D 183/07 C09D 183/07

Claims (19)

[Claims] 1. A polydialkylsiloxane having at least one polymerizable unsaturated group per molecule (a1), an organopolysilsesquioxane having a polymerizable unsaturated group (a2) and other polymerizable unsaturated groups (A)
3) and a copolymer resin (A) having two or more active hydrogens in the molecule, and a crosslinker having two or more reactive groups in the molecule capable of reacting with the active hydrogen to form a crosslinked structure. A resin composition for coating, characterized by containing an agent (B). 2. The resin composition for coating according to claim 1, wherein the polymerizable unsaturated group of the polydialkylsiloxane (a1) having at least one polymerizable unsaturated group per molecule is a vinyl group or a substituted vinyl group. Stuff. 3. The copolymer resin (A) contains 0.5 to 60% by weight of a component derived from (a1) and 0.5% by weight of a component derived from (a2).
-20% by weight, a component derived from (a3) in the range of 20-99.0% by weight, and a hydroxyl value of 10-130 (KO).
Hmg / g). 4. A compound having another polymerizable unsaturated group (a)
3) contains (meth) acrylic acid, and its content in the copolymer resin (A) is 0.5 to 5.0% by weight.
4. The coating resin composition according to any one of items 1 to 3. 5. The coating according to claim 1, wherein the number average molecular weight of the polydialkylsiloxane (a1) having at least one polymerizable unsaturated group per molecule is from 500 to 50,000. Resin composition. 6. The copolymer resin (A) according to claim 1 in an amount of 2 to 99% by weight, and the other copolymer resin (C) in an amount of 98 to 1% by weight. A coating resin composition, comprising: a composition; and a crosslinking agent (B) having two or more reactive groups in a molecule capable of forming a crosslinked structure by reacting with active hydrogen. 7. A copolymer resin (C) produced from an organopolysilsesquioxane (c1) having a polymerizable unsaturated group and another compound (c2) having a polymerizable unsaturated group. The coating resin composition according to claim 6. 8. The copolymer resin (C) contains 0.5 to 20% by weight of a component derived from (c1) and 80% of a component derived from (c2).
The coating resin composition according to claim 7, which is contained in an amount of from 9 to 99.5% by weight. 9. The copolymer resin (C) having a hydroxyl value of 10
The resin composition for coating according to any one of claims 6 to 8, wherein the amount is from 130 to 130 (KOHmg / g). 10. The reactive group of the crosslinking agent (B) having two or more reactive groups capable of forming a crosslinked structure by reacting with active hydrogen in the molecule is either isocyanate or melamine, or a combination thereof. The coating resin composition according to claim 1. 11. The resin composition for coating according to claim 10, wherein the crosslinking agent (B) having two or more reactive groups in a molecule capable of reacting with active hydrogen to form a crosslinked structure is an isocyanate compound. 12. The isocyanate compound is a urethane-modified isocyanate monomer, an allophanate-modified isocyanate,
The resin composition for coating according to claim 11, which is at least one selected from a modified isocyanurate, a modified buret, a modified carbodiimide, and a modified blocked isocyanate. 13. A resin composition for preventing graffiti or sticking paper, wherein the resin composition for coating according to any one of claims 1 to 12 is used as a top coat agent. 14. A resin composition for a back surface treating agent, comprising using the resin composition for a coating according to claim 1 as a back surface treating agent for an adhesive tape or a film. 15. The component derived from (a1) is 0.5 to 15% by weight, the component derived from (a2) is 0.5 to 20% by weight, and (meth) acrylic acid is 0.5 to 5.0% by weight. And a copolymer resin (A) having a hydroxyl value of 50 to 130 (KOHmg / g) and an isocyanate group of 0.5 to 1.5 equivalents to the hydroxyl group. The resin composition for a back surface treating agent according to claim 14, comprising a crosslinking agent (B). 16. The resin composition for coating according to claim 1, wherein the resin composition for coating is paper, processed paper, cloth, plastic product, plastic film, metal, porcelain tile, concrete, wood product, or coating thereof. 0.02 to 150 g on at least one side of the substrate selected from the product
/ M ² , a coating method characterized by coating. 17. The coating according to claim 16, wherein the resin composition for coating according to any one of claims 1 to 15 is applied to at least one surface of a substrate to a thickness of 0.05 to 10 g / m ^2. Construction method. 18. A laminate obtained by the coating method according to claim 16. Description: 19. A laminate according to claim 18, wherein the laminate is a protective film for protecting the surface.