JP2012172094A - Resin composition for molding, sheet, pressure-sensitive adhesive sheet, method for producing the sheet, and molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition, a sheet, a pressure-sensitive adhesive sheet, and a molded body that exhibit excellent toughness, flexibility, gasoline resistance, chemical resistance, molding processability, weather resistance, and temporal stability.SOLUTION: The resin composition for molding includes: an acrylic copolymer (A) having a weight-average molecular weight of 5,000-500,000; a polyisocyanate compound (B); and a compound (C) having a number-average molecular weight of 250-10,000, wherein the acrylic copolymer (A) is obtained by copolymerizing a (meth)acrylic monomer having an isocyanate group, a (meth)acrylic monomer having a hydroxy group, and another monomer, and the compound (C) is a compound selected from the group consisting of a polycarbonate, a polyester, and a polybutadiene.

Description

  The present invention relates to a molding resin composition, a cured product of the molding resin composition, a sheet and an adhesive sheet used for various decorations, displays, and packaging, a method for producing the sheet, and a molded body.

  Currently, plastic sheets are coated with adhesives and adhesives as necessary, and then colored and decorated on exterior panels, interior materials, building materials, various information boards, traffic signs, indoor / outdoor advertisements, signboards, shutters, windows, etc. It is used for the purpose of giving a display, or for the purpose of imparting various surface functions such as weather resistance, antifouling properties, rust prevention properties, various resistances and the like. On the other hand, as a packaging material, various plastic sheets are used for the purpose of imparting decorations and functions to articles. Alternatively, various plastic sheet moldings are used as parts for automobiles, motorcycles, motor boats, snowmobiles, home appliances, electronic devices, and the like.

  In many cases, a semi-rigid or soft vinyl chloride resin is used for these plastic sheet materials because of a good balance between strength and extensibility. However, a semi-rigid or soft vinyl chloride resin is added with a large amount of a low molecular weight compound such as a phthalic acid plasticizer in order to impart physical properties such as moldability, extensibility and flexibility. Yes. Since these plasticizers are low molecular weight, they have a high migration property.They migrate to the surface of the sheet over time, impair the appearance, lower the adhesive force by moving to the adherend, and blisters and wrinkles due to expansion of the sheet. It has a problem of generating. Further, when the plasticizer moves to the sheet surface or adherend, the extensibility of the sheet is lost, the state during molding cannot be maintained, and there is a problem that the appearance is blurred. . In addition, the soft vinyl chloride resin has a problem of low hardness and inferior wear resistance and scratch resistance.

  On the other hand, since vinyl chloride resin contains chlorine in the resin, it has been pointed out that if it is not incinerated under suitable conditions, highly toxic dioxins may be generated as a by-product during incineration. In addition, the durability in the furnace may be lowered by hydrochloric acid generated even when incinerated at a sufficiently high temperature, and many requirements are required for the structure and operation of the incinerator. For this reason, there is an increasing demand for plastic films with less environmental impact.

  As other plastic sheet materials, acrylic resins such as polymethyl methacrylate, polyester resins such as polyethylene terephthalate, and polyolefin resins such as polyethylene and polypropylene are generally known. However, acrylic resins such as polymethyl methacrylate and polyester resins such as polyethylene terephthalate have toughness, but are inferior in extensibility. As with the vinyl chloride resin, a low molecular weight plasticizer must be added. Further, these resins have a problem that when the molecular weight is increased, the dispersibility of a colorant such as a pigment is lowered, so that coloring becomes difficult and decorative properties cannot be obtained. On the other hand, when the molecular weight of the resin is lowered, the pigment dispersibility is improved, but there is a problem that the sheet has poor toughness.

  Therefore, as an example of solving the above problems, a plastic sheet made of an acrylic polymer obtained by graft polymerization of polyether, polyester, etc., polyether, polyester, etc., and a cured product of a resin composition containing polyisocyanate is disclosed. (See Patent Document 1). Such an acrylic resin film has a certain toughness, is excellent in stretchability and colorability, and has a weather resistance superior to that of vinyl chloride resin, so it is a marking film for indoor and outdoor use. It is used as

  However, since the acrylic resin film in the present invention is inferior to vinyl chloride resin in terms of toughness as a coating film when used as a marking film, improvement in tear characteristics has been desired. Further, when used in automobiles, motorcycles, etc., there is a problem that defects in appearance such as swelling and coloring of the sheet due to contact with gasoline during refueling occur.

International Publication No. WO2002 / 057332

  However, since the acrylic resin film in Patent Document 1 is inferior to vinyl chloride resin in terms of toughness as a coating film when used as a marking film, improvement in tear characteristics has been desired. Further, when used in automobiles, motorcycles, etc., there is a problem that defects in appearance such as swelling and coloring of the sheet due to contact with gasoline during refueling occur.

  The present invention is a molding resin composition which is a chlorine-free resin and does not contain a plasticizer, and has excellent toughness, flexibility, gasoline resistance, chemical resistance, molding processability, weather resistance, aging To provide a molding resin composition exhibiting stability, a cured product of the molding resin composition, a sheet and an adhesive sheet used for various decorations and displays, packaging, a manufacturing method of the sheet, and a molded body is there.

  The present inventors use a polyfunctional polyisocyanate compound for forming a dense cross-linked structure as a second component, using an acrylic polymer containing an isocyanate group and a hydroxyl group having toughness and high weather resistance as a first component. A resin composition comprising a compound selected from polyester, polycarbonate, or polybutadiene containing two or more functional groups capable of reacting with an isocyanate group as a third component as a component and further imparting flexibility and extensibility. It has been found that it has extremely excellent sheet characteristics, and has led to the present invention.

  The present invention includes an (meth) acrylic monomer having an isocyanate group and a (meth) acrylic monomer having a hydroxyl group as essential components, and is copolymerized with another (meth) acrylic monomer. An acrylic copolymer (A) having a weight average molecular weight of 5,000 to 500,000, a polyisocyanate compound (B), two or more functional groups capable of reacting with an isocyanate group, and a number average molecular weight of 250. The present invention relates to a molding resin composition comprising at least one compound (C) selected from polycarbonate, polyester, and polybutadiene having a molecular weight of 10,000 to 10,000.

  In the acrylic copolymer (A), the content of the (meth) acrylic monomer having an isocyanate group constituting the copolymer is 1 to 1 of the total amount of the (meth) acrylic monomer. 10% by weight and the content of the (meth) acrylic monomer having a hydroxyl group is 1 to 10% by weight of the total amount of the (meth) acrylic monomer. The present invention relates to a resin composition.

  Further, the present invention is characterized by containing 10 to 50 parts by weight of the polyisocyanate compound (B) and 10 to 100 parts by weight of the compound (C) with respect to 100 parts by weight of the acrylic copolymer (A). The present invention relates to a molding resin composition of the above invention.

  Moreover, this invention is a group which consists of an oxime compound, a lactam compound, a phenol compound, an active methylene compound, a heterocyclic compound, and an amino compound with respect to 100 mol% of isocyanate groups of an acrylic copolymer (A) and a polyisocyanate compound (B). The present invention relates to the molding resin composition according to the invention, characterized in that the functional group of any one of the compounds (D) selected is reacted in an amount of 10 to 100 mol%.

  In the present invention, 1 to 10% by weight of a (meth) acrylic monomer having an isocyanate group and 1 to 10% by weight of a (meth) acrylic monomer having a hydroxyl group are copolymerized with another monomer. Step (1) for obtaining an acrylic copolymer (A) having an isocyanate group and a hydroxyl group having a weight average molecular weight of 5,000 to 500,000, and the isocyanate group of the resulting acrylic copolymer (A) 10-100 mol% of functional groups of any compound (D) selected from the group consisting of oxime compounds, lactam compounds, phenolic compounds, active methylene compounds, heterocyclic compounds and amino compounds are reacted with respect to 100 mol%. The step (2) of obtaining the acrylic copolymer (A-2) with, with respect to 100 mol% of the isocyanate group of the isocyanate compound (B), the oxy An isocyanate compound (B-2) by reacting 10 to 100 mol% of a functional group of any compound (D) selected from the group consisting of a compound, a lactam compound, a phenol compound, an active methylene compound, a heterocyclic compound and an amino compound ), The group consisting of 10 to 50 parts by weight of an isocyanate compound (B-2), polycarbonate, polyester and polybutadiene with respect to 100 parts by weight of the obtained acrylic copolymer (A-2). A method for producing a molding resin composition comprising the step (4) of blending 10 to 100 parts by weight of the compound (C), which is one or more selected, and obtaining the resin composition by stirring. About.

Moreover, this invention relates to the manufacturing method of the resin composition for shaping | molding of the said invention characterized by further mix | blending a coloring agent in a process (4).
The present invention also relates to the molding resin composition according to the invention, further comprising a colorant.

  Moreover, this invention relates to the sheet | seat formed by shape | molding the resin composition for molding obtained from the resin composition for molding of the said invention, or the manufacturing method of the resin composition for molding of the said invention.

  Moreover, this invention relates to the adhesive sheet characterized by having the sheet | seat of the said invention and an adhesive layer.

  The present invention also relates to a molded product formed by molding a sheet or a pressure-sensitive adhesive sheet obtained by molding the molding resin composition of the above invention or the molding resin composition obtained by the production method of the above invention.

  According to the present invention, a sheet having toughness, flexibility, gasoline resistance, chemical resistance and molding processability comparable to that of a vinyl chloride resin-based sheet and having weather resistance and temporal stability that surpasses that of a vinyl chloride resin-based sheet. A moldable resin composition that can be molded can be provided.

  The molding resin composition of the present invention comprises an acrylic copolymer (A) having a weight average molecular weight of 5,000 to 500,000 (hereinafter also referred to as polymer (A)) and a polyisocyanate compound (B And a compound (C) having a number average molecular weight of 250 to 10,000.

  The polymer (A) is obtained by copolymerizing a (meth) acrylic monomer having an isocyanate group, a (meth) acrylic monomer having a hydroxyl group, and another monomer. The polymer (A) is used to impart toughness, weather resistance, gasoline resistance, and chemical resistance to the sheet when the molding resin composition is molded as a sheet. Serves as a hard segment.

  As the (meth) acrylic monomer having an isocyanate group, 2-acryloyloxyethyl isocyanate (trade name: Karenz AOI, manufactured by Showa Denko KK), 2-methacryloyloxyethyl isocyanate (trade name: Karenz MOI, Showa) Denko Co., Ltd.), 1,1-bis (acryloyloxymethyl) ethyl isocyanate (trade name: Karenz BEI, Showa Denko Co., Ltd.) and the like. Also, “Karenz MOI-BM” (Showa Denko Co., Ltd.) in which the isocyanate group of 2-methacryloyloxyethyl isocyanate is blocked with an amine compound, and “Karenz MOI-BP” (Showa Denko Co., Ltd.) blocked with a pyrazole compound. ) Etc. can also be used.

  Examples of the (meth) acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, and the like.

  Other than the (meth) acrylic monomer having an isocyanate group and the (meth) acrylic monomer having a hydroxyl group, an alkyl (meth) acrylate, an aromatic vinyl monomer, an isocyanate group And (meth) acrylic monomers having functional groups other than hydroxyl groups are preferred.

  Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, and lauryl (meth). Examples include alkyl (meth) acrylates such as acrylate.

  Examples of the aromatic vinyl monomer include styrene, methyl styrene, and ethyl styrene. When using an aromatic vinyl monomer among these monomers, it is desirable to keep it to the minimum necessary amount from the viewpoint of weather resistance.

  The functional group of the (meth) acrylic monomer having a functional group other than an isocyanate group and a hydroxyl group is preferably an amino group, a carboxyl group, an epoxy group, an N-methylol group, an N-alkoxymethyl group, or the like.

  For example, as a (meth) acrylic monomer having an amino group, methylaminoethyl (meth) acrylate, ethylaminoethyl (meth) acrylate, butylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, etc. N, N-dialkyl such as monoalkylaminoalkyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylamino (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate An aminoalkyl (meth) acrylate etc. are mentioned.

  Examples of the (meth) acrylic monomer having a carboxyl group include acrylic acid and methacrylic acid.

  Examples of the (meth) acrylic monomer having an epoxy group include glycidyl (meth) acrylate.

  Examples of the (meth) acrylic monomer having an N-methylol group include N-methylol (meth) acrylamide.

  Examples of the (meth) acrylic monomer having an N-alkoxymethyl group include N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-butoxymethyl ( (Meth) acrylamide and other (meth) acrylamides having N-monoalkoxymethyl groups, N, N-dimethylol (meth) acrylamide, N, N-di (methoxymethyl) (meth) acrylamide, N, N-di (ethoxymethyl) ) (Meth) acrylamide, N, N-di (propoxymethyl) (meth) acrylamide, (meth) acrylamide having an N, N-dialkoxymethyl group such as N, N-di (butoxymethyl) (meth) acrylamide Is mentioned.

  The polymer (A) can be obtained by a known method such as solution polymerization. Solvents include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol methyl ether, diethylene glycol methyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, Ethers such as diethylene glycol dimethyl ether, hydrocarbons such as hexane, heptane and octane, aromatics such as benzene, toluene, xylene and cumene, and esters such as ethyl acetate and butyl acetate can be used. Two or more solvents may be mixed and used.

  The polymerization initiator used for the synthesis of the polymer (A) is a peroxide or an azo compound such as benzoyl peroxide, azoisobutylvaleronitrile, azobisisobutyronitrile, di-t-butyl peroxide, t-butyl perbenzoate. , T-butyl peroctoate, cumene hydroxyperoxide and the like can be used, and the reaction temperature is preferably 50 to 200 ° C, particularly preferably 70 to 140 ° C.

  The weight average molecular weight of the polymer (A) is preferably 5,000 to 500,000, more preferably 10,000 to 100,000. When the weight average molecular weight of the copolymer (a) exceeds 500,000, the extensibility of the obtained sheet is lowered, whereas when it is less than 5,000, the toughness and chemical resistance of the obtained sheet are low. Become. In the present invention, the weight average molecular weight refers to a weight average molecular weight in terms of polystyrene obtained by preparing a calibration curve using a polystyrene resin having a predetermined molecular weight by gel permeation chromatography and measuring the molecular weight.

  The glass transition temperature of the polymer (A) is preferably 0 to 120 ° C, more preferably 30 to 90 ° C. If the glass transition temperature of the copolymer (a) exceeds 120 ° C, the extensibility of the resulting sheet may be reduced. On the other hand, when the temperature is lower than 30 ° C., chemical resistance and surface hardness of the obtained sheet may be lowered.

  The content of the (meth) acrylic monomer having an isocyanate group in the total (meth) acrylic monomer used for copolymerization is preferably 1 to 10% by weight, and the (meth) acrylic monomer having a hydroxyl group The content of is also preferably 1 to 10% by weight. If the content of the (meth) acrylic monomer containing each functional group is less than 1% by weight, the functional group concentration of the polymer (A) is insufficient. It is difficult to ensure the strength. On the other hand, when the content of the functional group-containing (meth) acrylic monomer is higher than 10% by weight, the crosslinking density becomes excessive, and the sheet tends to be difficult to obtain the flexibility and molding processability.

  In the present invention, the polyisocyanate compound (B) (hereinafter also referred to as compound (B)) is used as a sheet to impart performances such as toughness, gasoline resistance, and chemical resistance of the coating film, and for molding. It plays a role as a crosslinking component in the resin composition.

  In the present invention, the compound (B) is an isocyanate compound having two or more isocyanate groups. The compound (B) is preferably an alicyclic isocyanate compound, an aliphatic isocyanate compound, an aromatic isocyanate compound or the like.

  Examples of the alicyclic isocyanate compound include isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, and the like.

  Examples of the aliphatic isocyanate compound include trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaproate, 4,4′-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, 1,3,6-hexamethylene triisocyanate. Etc.

  Examples of the aromatic isocyanate compound include diphenylmethane diisocyanate, toluylene diisocyanate, naphthylene-1,5-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate. Etc. Moreover, the both-ends isocyanate adduct body, biuret modified body, isocyanurate modified body of an isocyanate compound and glycols or diamines can be mentioned. Among these compounds, the use of alicyclic or aliphatic isocyanate compounds is desirable from the viewpoint of reactivity, weather resistance, and yellowing, and more isocyanurate modified products, particularly when an isocyanurate ring-containing triisocyanate is included. A tough and extensible sheet can be obtained.

  As the isocyanurate ring-containing triisocyanate, specifically, isocyanurate-modified isophorone diisocyanate (for example, Desmodur Z4470 manufactured by Sumitomo Bayer Urethane Co., Ltd.), isocyanurate-modified hexamethylene diisocyanate (for example, manufactured by Sumitomo Bayer Urethane Co., Ltd.) Sumijour N3300).

  Moreover, you may use the block modified body which made the isocyanate group of the said isocyanate compound react with a blocking agent, and was blocked.

  Even if it is normal temperature, the resin composition for shaping | molding may advance a reaction of a compound (B) and a polymer (A), and a viscosity may increase with progress of time. Therefore, for the purpose of improving the viscosity stability, the compound (B) using a compound (D) (hereinafter also referred to as a blocking agent) such as an oxime compound, a lactam compound, a phenol compound, an active methylene compound, a heterocyclic compound and an amino compound. ) And the isocyanate group of the polymer (A) can be blocked.

The blocking agent is desirably one that causes dissociation of the blocking agent from the isocyanate group at a relatively low temperature. As such compounds, oxime compounds, lactam compounds, phenol compounds, active methylene compounds, pyrazole compounds, imidazoles, heterocyclic compounds, amino compounds and the like are preferable. For example,
Examples of the oxime compound include formamide oxime, acetamide oxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, benzophenone oxime, and cyclohexanone oxime.
Examples of the lactam compound include caprolactam, valerolactam, butyrolactam, and propiolactam.
Examples of the phenol compound include phenol, cresol, xylenol, and ethylphenol.
Active methylene compounds such as dimethyl malonate, diethyl malonate, dipropyl malonate, diisopropyl malonate, dibutyl malonate, methyl ethyl malonate, methyl ethyl malonate, methyl butyl malonate, ethyl propyl malonate, Examples include malonic acid esters such as ethyl malonate, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, isopropyl acetoacetate, acetoacetate such as butyl acetoacetate, and acetylacetone.
Pyrazole compounds such as pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, 3-methyl-5-phenylpyrazole Is mentioned.

  Examples of imidazole include imidazole, benzimidazole, 2-methylimidazole, 2-ethylimidazole and the like.

  Examples of the heterocyclic compound include 1,2,4-triazole.

  Examples of the amino compound include diisopropylamine, dicyclohexylamine, di-t-butylamine, piperidine, and 2,2,6,6-tetramethylpiperidine.

  Moreover, you may use the commercially available block modified body which blocked the isocyanate group of the compound (B) previously. Examples of such compounds include 7951 manufactured by Baxen Chemicals Limited, in which the isocyanate group of isocyanurate-modified isophorone diisocyanate is blocked with 3,5-dimethylpyrazole, and the isocyanate group of isocyanurate-modified isophorone diisocyanate is blocked with diisopropylamine. Evonik Degussa Japan Co., Ltd. VESTANAT EP-B 1299 and the like. In these compounds, the isocyanate group is completely blocked by a blocking agent.

  Furthermore, as the compound (B), a compound selected from the group consisting of polyether, polyester, polycarbonate, or polybutadiene having two or more functional groups capable of reacting with an isocyanate group, and an isocyanate compound having an isocyanate group at both ends, You may use the both-ends isocyanate prepolymer which made this react. When the compound (B) contains the above-mentioned both-end isocyanate prepolymer, extensibility is obtained with a small amount, and the toughness of the sheet is not impaired.

  In the present invention, the compound (C) is a compound having a number average molecular weight of 250 to 10,000 selected from the group consisting of polycarbonate, polyester, and polybutadiene, having two or more functional groups capable of reacting with an isocyanate group. The compound (C) exhibits a function as a soft segment in the molding resin composition that imparts flexibility and extensibility to the sheet. The compound (C) is necessary for the sheet without elution and precipitation with the lapse of time like a sheet using a plasticizer by crosslinking reaction with the polymer (A) and the compound (B). Flexibility and extensibility can be imparted.

  As the functional group capable of reacting with the isocyanate group of the compound (C), a hydroxyl group, amino group, carboxyl group, epoxy group, N-methylol group, N-alkoxymethyl group and the like are preferable. Among these, a hydroxyl group is more preferable in terms of crosslinking reactivity and molding processability of the obtained sheet.

  As the compound (C), for example, a polycarbonate, polyester, or polybutadiene having one or more functional groups capable of reacting with an isocyanate group at the end of the molecule, whether linear or branched, can be used. Of these, polycarbonate is preferred from the viewpoint of the balance of extensibility, toughness and molding processability of the obtained sheet.

Examples of the polycarbonate include polycarbonate diol and a carbonate compound in which a terminal hydroxyl group is modified with an amino group, a carboxyl group, an epoxy group, an N-methylol group, or an N-alkoxymethyl group. The polycarbonate diol represented is particularly preferred.
H- (O-R-OCO-) nR-OH General formula (1)
(R is a divalent alkylene group, and n is an integer of 1 to 20.)
Examples of the commercially available polycarbonate diol include, for example, Kuraray Polyol PMHC-590, PMHC-1050, PMHC-1050R, PMHC-1090, PMHC-2050, PMHC-2050R, PMHC-2070R, PMHC-2070R, PMHC- manufactured by Kuraray Co., Ltd. 2090, PMHC-2090R, PMHC-5090, and others include T4691, T5692, T4671, T4672, T5650E, T5650J, T5651 and T5652 manufactured by Asahi Kasei Chemicals Corporation.

  Examples of polyesters include terminal hydroxyl group-containing ester compounds obtained by esterifying at least one dicarboxylic acid and at least one polyol such as a polyhydric alcohol, a polyhydric phenol, or an alkoxy modified product thereof, and a terminal. And an ester compound in which the hydroxyl group is modified to an amino group, a carboxyl group, an epoxy group, an N-methylol group, or an N-alkoxymethyl group.

  As polyester (polyester polyol) which has two or more hydroxyl groups of a commercial item, for example, Kuraray Polyol P-510, P-1010, P-1510, P-2010, P-3010, P-3010, manufactured by Kuraray Co., Ltd. P-5010, P-6010, P-2011, P-2013, P-520, P-1020, P-2020, P-1012, P-2012, P-530, P-1030, P-2030, PMHC- 2050, PMHC-2050R, PMHC-2070, PMHC-2090, PMSA-1000, PMSA-2000, PMSA-3000, PMSA-4000, F-2010, F-3010, N-2010, PNOA-1010, PNOA-2014, O-2010, Desmofe made by Sumitomo Bayer Urethane Co., Ltd. 650MPA, 651MPA / X, 670, 670BA, 680X, 680MPA, 800, 800MPA, 850, 1100, 1140, 1145, 1150, 1155, 1200, 1300X, 1652, 1700, 1800, RD181, RD181X, C200, Toyobo Co., Ltd. Byron 200, 560, 600, GK130, GK860, GK870, 290, GK590, GK780, GK790, and the like are available.

  Examples of polybutadiene include α, ω-polybutadiene glycol, α, β-polybutadiene glycol, and butadiene having a terminal hydroxyl group modified with an amino group, a carboxyl group, an epoxy group, an N-methylol group, or an N-alkoxymethyl group. Compounds.

  Examples of the commercially available polybutadiene having two or more hydroxyl groups include NISSO-PB G-1000, G-2000, G-3000, GI-1000, GI-2000, GI-3000, and GQ-1000 manufactured by Nippon Soda Co., Ltd. , GQ-2000 and the like. Examples of the polybutadiene having two or more commercially available epoxy groups include NISSO-PB BF-1000, EPB-13, and EPB-1054 manufactured by Nippon Soda Co., Ltd.

  The molecular weight of the compound (C) is preferably 250 to 10,000, more preferably 500 to 5,000. When the molecular weight of the compound (C) exceeds 10,000, the solubility in a solvent and the compatibility with the polymer (A) tend to decrease, and the toughness of the resulting sheet tends to decrease. . On the other hand, when the molecular weight is less than 500, the stretchability and flexibility of the sheet may be insufficient.

  The ratio of using the polymer (A), the compound (B) and the compound (C) is desirably in the range of A) to (B) to (C) = 100 to 10 to 50 to 10 to 100 by weight ratio.

  When the ratio (B) is reduced from this range, or when the ratio (C) is increased from this range, the toughness, gasoline resistance, and chemical resistance of the resulting sheet may be lowered. When the ratio (B) is increased from this range, or when the ratio (C) is decreased from this range, the flexibility and extensibility of the obtained sheet may be lowered. Even when the ratios (B) and (C) are both increased or decreased, it is difficult to obtain a balance between curability and coating film performance.

  The molding resin composition of the present invention can contain various crosslinking catalysts in order to promote the crosslinking reaction. Typical crosslinking catalysts include organometallic compounds, acids and their ammonium salts, lower amine salts, polyvalent metal salts, amines, organic peroxides and the like.

  Specific examples of organometallic compounds include sodium acetate, tin octylate, lead octylate, cobalt octylate, zinc octylate, calcium octylate, lead naphthenate, cobalt naphthenate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin Examples thereof include malate, dibutyltin di (2-ethylhexoate), diethylzinc, and tetra (n-butoxy) titanium.

  Specific examples of the acid include trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, phosphoric acid ester of β-hydroxyethyl (meth) acrylate, monoalkyl phosphorous acid, dialkyl phosphorous acid, p-toluenesulfone Examples include acid, phthalic anhydride, benzoic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, formic acid, acetic acid, propionic acid, itaconic acid, oxalic acid, maleic acid and the like.

  Specific examples of amines include dicyclohexylamine, triethylamine, N, N-dimethylbenzylamine, N, N, N ′, N′-tetramethyl-1,3-butanediamine, diethanolamine, triethanolamine, cyclohexylethylamine and the like. Is mentioned.

  Organic peroxides include hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, cyclohexanone peroxide, di-t-butyl peroxide, dicumyl peroxide, diacetyl peroxide, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate , T-butyl peroxylaurate and the like.

  Two or more kinds of these crosslinking catalysts may be used, and 0.001 to 5 parts by weight is preferable with respect to 100 parts by weight in total of the polymer (A), the compound (B) and the compound (C). More preferred is 3 parts by weight.

  The molding resin composition of the present invention preferably contains various colorants such as pigments and dyes as long as the effects of the present invention are not hindered.

  Examples of pigments include quinacridone, anthraquinone, perylene, perinone, diketopyrrolopyrrole, isoindolinone, condensed azo, benzimidazolone, monoazo, insoluble azo, naphthol, and flavan. Organic pigments such as throne, anthrapyrimidine, quinophthalone, pyranthrone, pyrazolone, thioindigo, anthanthrone, dioxazine, phthalocyanine, and indanthrone, and metal complexes such as nickel dioxin yellow and copper azomethine yellow Metal oxides such as titanium oxide, iron oxide and zinc oxide, metal salts such as barium sulfate and calcium carbonate, inorganic pigments such as carbon black, aluminum and mica, metal fine powder such as aluminum, and mica fine powder.

  Examples of the dye include azo series, quinoline series, stilbene series, thiazole series, indigoid series, anthraquinone series, and oxazine series.

  In the present invention, particularly when a pigment is added, a colorant, a dispersion resin, and a pigment paste in which a dispersant and a solvent are mixed are first prepared and then mixed with other components. preferable. As the dispersion resin, the compound (C) is preferably used, but is not particularly limited, and has a polar group excellent in pigment dispersibility, such as a hydroxyl group, a carboxyl group, a thiol group, an amino group, an amide group, and a ketone group. An acrylic resin, a polyurethane resin, a polyurea resin, a polyester resin, or the like can be used. Examples of the dispersant include pigment derivatives, anionic surfactants, amphoteric surfactants, nonionic surfactants, titanium coupling agents, and silane coupling agents. In addition, the pigment surface can be modified by metal chelate, resin coating, or the like.

  Moreover, in order to raise the intensity | strength of a sheet | seat, in the resin composition for shaping | molding of this invention, if it is a range which does not prevent the effect of this invention, you may contain various thermoplastic resins.

  Examples of the thermoplastic resin include polypropylene, polyethylene, ethylene-vinyl acetate copolymer, polyisobutylene, polybutadiene, polystyrene, polycarbonate, polymethylpentene, ionomer, acrylonitrile-butadiene-styrene resin, acrylic resin, polyvinyl alcohol, Examples thereof include polyamide resin, polyacetal, and polyester.

  The molding resin composition of the present invention can further use a solvent.

  Solvents include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol ethyl ether, diethylene glycol ethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol Depending on the composition of the resin composition from ethers such as dimethyl ether, hydrocarbons such as hexane, heptane and octane, aromatics such as benzene, toluene, xylene and cumene, and esters such as ethyl acetate and butyl acetate Use an appropriate one. Two or more solvents may be used.

  Further, the molding resin composition of the present invention, if necessary, as long as it does not interfere with the effects of the present invention, UV absorber, light stabilizer, radical scavenger, filler, thixotropy imparting agent, aging Antioxidants, antioxidants, antistatic agents, flame retardants, thermal conductivity improvers, plasticizers, anti-sagging agents, antifouling agents, antiseptics, bactericides, antifoaming agents, leveling agents, antiblocking agents, curing agents Various additives such as a thickener, a pigment dispersant, and a silane coupling agent may be added.

  In addition, the molding resin composition includes the step (1) of obtaining the polymer (A) by known solution polymerization as described above, and the isocyanate group of the obtained polymer (A) is converted into an oxime compound, a lactam compound, a phenol compound, Step (2) for obtaining a polymer (A-2) blocked with any compound (D) selected from the group consisting of an active methylene compound, a heterocyclic compound and an amino compound, the isocyanate group of the isocyanate compound (B) Step (3) for obtaining a compound (B-2) blocked with any compound (D) selected from the group consisting of an oxime compound, a lactam compound, a phenol compound, an active methylene compound, a heterocyclic compound and an amino compound, 10 to 50 parts by weight of compound (B-2) and 10 to 100 parts by weight of compound (C) with respect to 100 parts by weight of combined (A-2) And it can be obtained via stirring to step (4).

  Further, the molding resin composition of the present invention is preferably obtained by mixing a colorant, a crosslinking catalyst, an additive, and a solvent in addition to the polymer (A), the compound (B), and the compound (C).

  Solvents include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol ethyl ether, diethylene glycol ethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol Depending on the composition of the resin composition from ethers such as dimethyl ether, hydrocarbons such as hexane, heptane and octane, aromatics such as benzene, toluene, xylene and cumene, and esters such as ethyl acetate and butyl acetate Use an appropriate one. Two or more solvents may be used.

  The sheet of the present invention is formed by molding the above molding resin composition into a sheet shape. The sheet molding method can be obtained, for example, by applying a molding resin composition on a release sheet, curing the film, and forming a film. As the release sheet, for example, a paper subjected to a release treatment on one or both sides, a plastic film such as polyester, polypropylene, polyethylene, and cellulose acetate, a metal foil such as aluminum and stainless steel, and the like can be used. The thing of 10-250 micrometers is used suitably.

  The above coating is a conventionally known method such as gravure coating method, kiss coating method, die coating method, lip coating method, comma coating method, blade coating method, roll coating method, knife coating method, curtain coating method, slot orifice method, spraying. It can be performed by a coating method, a bar coating method, or the like. The resin composition may be applied in several times, or may be applied once. A plurality of different methods may be combined.

  The thickness of the sheet is usually about 10 to 250 μm, but is not limited to this range, and may be applied so as to have a thickness suitable for the application and required performance.

  Although the said hardening is normally performed at room temperature-350 degreeC, the range of 30-350 degreeC is preferable from the point of the efficiency improvement and productivity improvement of hardening.

  It is preferable to provide an adhesive layer on one or both sides of the sheet of the present invention. Examples of the adhesive include rubber-based adhesives mainly composed of general natural rubber, synthetic isoprene rubber, recycled rubber, styrene-butadiene rubber, polyisoprene rubber, styrene-isoprene-styrene rubber, and (meth) Acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, silicones mainly composed of polymers obtained by copolymerizing monomers such as acrylic acid, methacrylic acid, acrylamide, vinyl acetate, and styrene mainly composed of acrylic acid esters (C2 to C12) An adhesive having a suitable adhesive strength can be selected according to the use and the material of the adherend.

  Depending on the type of adhesive and the coating suitability, the pressure-sensitive adhesive layer may be a conventionally known method such as a kiss coating method, a die coating method, a lip coating method, a comma coating method, a blade coating method, or a bar coating method. Utilizing it, it may be applied directly on the sheet and laminated, or the adhesive once coated on the process paper may be laminated on the sheet and laminated.

  Sheets of the present invention are exterior boards, interior materials, building materials, various information boards, traffic signs, indoor / outdoor advertisements, signboards, shutters, windows, etc., as various decorations, coloring, display materials, and weather resistance, It is used as a sheet for imparting various surface functions such as antifouling properties and various resistances, and as a packaging material for preventing the deterioration of the quality of various articles and protecting each function.

  The molded product of the present invention can be obtained by molding the above sheet.

  The form of the molded product is (1) a molded product composed of only a sheet. (2) A sheet in which a sheet, an adhesive layer, and a resin sheet are sequentially laminated. (3) The lamination sheet etc. which laminated | stacked the hardened | cured material of the resin composition of this invention containing a coloring agent on the resin sheet are used.

  Examples of the resin constituting the resin sheet include acrylic resins; polyolefin resins such as polyethylene, polypropylene, polyvinyl chloride, polyvinyl acetate, polyvinyl chloroacetate, polyvinyl fluoride, and polyvinylidene fluoride resins; and copolymers thereof; polyethylene terephthalate. Polyester resins such as polycarbonate resins, polystyrene resins and the like can also be used.

  Among these, an acrylic resin sheet is most desirable from the viewpoint of recycling. Specifically, it is a copolymer of polymethyl methacrylate or other acrylic resins. Examples of the copolymer include an ethylene-methyl methacrylate copolymer, an ethylene-methyl acrylate copolymer, and an ethylene-ethyl acrylate copolymer.

  In the present invention, the resin sheet includes a relatively thin sheet generally called a film or sheet to a thick sheet called a plate. The specific thickness is 10 μm to 10 mm, preferably about 20 to 100 μm in the case of a sheet, and preferably about 3 mm to 6 mm in the case of a plate. In the case of an acrylic board, there are clear and transparent ones which are completely colorless and milky white, and both are suitable.

  Moreover, since a resin sheet shape | molds after that, it is preferable that the softening point temperature as resin is 40-200 degreeC, More preferably, it is 80-150 degreeC.

  Desirably, the elongation of molding at the time of molding in the present invention is 101% to 500%. If it is 100% (that is, unstretched), there is no meaning, and if it is 500% or more, the colored film for molding is broken, and it cannot withstand the elongation of molding.

The molding method used in the present invention is not particularly limited, but generally known molding methods such as insert injection molding method, in-mold (in-mold) molding method, extrusion molding, vacuum / pneumatic molding method, blow molding (Blow molding), press molding, etc. are particularly useful.
Examples of the molded body thus obtained include parts (for example, bumpers) used for automobiles, motorcycles, motor boats, snowmobiles, home appliances, electronic devices, and the like.

  Hereinafter, the present invention will be described in detail by way of examples. In the examples, all parts and% indicate parts by weight and% by weight. Moreover, the weight average molecular weights of the obtained polymer etc. were measured as a polystyrene conversion value using a gel permeation chromatography (GPC) apparatus. As the GPC apparatus, Shimadzu high-performance liquid chromatograph Prominence GPC system manufactured by Shimadzu Corporation is used, GPC KF-804L + GPC KF-801 is used as the column at a column temperature of 40 ° C., and the solvent (mobile phase) is used. Tetrohydrofuran was measured at a flow rate of 0.80 mL / min using a differential refractive index detector as a detector.

(Synthesis Examples A1 to A18)
(Meth) acrylic monomer having isocyanate group, (meth) acrylic monomer having hydroxyl group, other (meth) acrylic in four-necked flask equipped with cooling tube, stirring device, thermometer, nitrogen introducing tube A monomer and a solvent were charged based on the blending ratio (part by weight ratio) shown in Table 1, and the temperature was raised to 90 ° C. with stirring in a nitrogen atmosphere, and a polymerization initiator (azobisisobutyronitrile: AIBN) was added. 70% by weight of the blending ratio shown in Table 1 is added to carry out a polymerization reaction for 2 hours, and then 15% of the blending ratio (part by weight) shown in Table 1 is added for azobisisobutyronitrile for another 2 hours. A polymerization reaction is carried out, and azobisisobutyronitrile is further added at 15% by weight of the blending ratio (parts by weight) shown in Table 1, and the polymerization reaction is further carried out for 2 hours to obtain a solution of acrylic copolymer (A). It was. Table 1 shows the weight average molecular weight (Mw) and glass transition temperature (Tg) of the obtained polymer (A).

AOI: 2-acryloyloxyethyl isocyanate (trade name: Karenz AOI, manufactured by Showa Denko KK)
MOI: 2-methacryloyloxyethyl isocyanate (trade name: Karenz MOI, manufactured by Showa Denko KK)
MOI-BM: amine block of 2-methacryloyloxyethyl isocyanate (trade name: Karenz MOI-BM, manufactured by Showa Denko KK)
MOI-BP: Pyrazole block of 2-methacryloyloxyethyl isocyanate (trade name: Karenz MOI-BP, manufactured by Showa Denko KK)
4-HBA: 4-hydroxybutyl acrylate HEMA: 2-hydroxyethyl methacrylate MMA: methyl methacrylate BMA: n-butyl methacrylate Xyl: xylene BuAc: butyl acetate

(Examples 1-35, Comparative Examples 1-6)
Compound (B), compound (C), and additive are mixed with the polymer (A) shown in Table 1 so as to have a ratio shown in Table 2 in terms of nonvolatile content, and toluene / butyl acetate = 50/50. A resin composition solution was prepared by diluting with a mixed solvent (weight ratio) so that the non-volatile content concentration was 60%.

  The equivalent ratio shown in Table 2 was [total number of moles of isocyanate groups in (A) and (B)] / [number of moles of isocyanate group-reactive functional groups in compound (C)].

PMHC-2050: Polycarbonate polyol (Kuraray Co., Ltd. “Kuraray Polyol PMHC-2050”, Mw = 2000)
T-5562: Polycarbonate polyol ("Duranol T-5552" manufactured by Asahi Kasei Chemicals Corporation, Mw = 2000)
T-5651: Polycarbonate polyol ("Duranol T-5651" manufactured by Asahi Kasei Chemicals Corporation, Mw = 1000)
T-5650J: Polycarbonate polyol ("Duranol T-5650J" manufactured by Asahi Kasei Chemicals Corporation, Mw = 800)
T-5650E: Polycarbonate polyol ("Duranol T-5650E" manufactured by Asahi Kasei Chemicals Corporation, Mw = 500)
P-3010: Polyester polyol (Kuraray Co., Ltd. “Kuraray polyol P-3010”, Mw = 3000)
F-3010: Polyester polyol (“Kuraray polyol F-3010” manufactured by Kuraray Co., Ltd., Mw = 3000)
G-2000: Polybutadiene polyol (“NISSO-PB G-2000” manufactured by Nippon Soda Co., Ltd., Mn = 2000)
Epol: Hydrogenated polybutadiene polyol (“Epol” manufactured by Idemitsu Kosan Co., Ltd., Mw = 2000)
BF-1000: Epoxy-modified polybutadiene polyol (“NISSO-PB BF-1000” manufactured by Nippon Soda Co., Ltd., Mw = 1000)
GK870: Polyester polyol (Toyobo Co., Ltd. “Byron GK870”, Mw = 13000)
1,12-DD: 1,12-dodecanediol (Mn = 202)
Z4470: Isocyanurate-modified isophorone diisocyanate (“Death Module Z4470” manufactured by Sumitomo Bayer Urethane Co., Ltd.)
N3300: Isocyanurate-modified hexamethylene diisocyanate (“Sumijoule N3300” manufactured by Sumitomo Bayer Urethane Co., Ltd.)
7951: 3,5-dimethylpyrazole blocked isocyanurate-modified isophorone diisocyanate (manufactured by Baxenden Chemicals Limited)
1299: Diisopropylamine blocked isocyanurate-modified isophorone diisocyanate (“VESTANAT EP-B 1299” manufactured by Evonik Degussa Japan)
Red: Red pigment (“Cincacia Magenta BRT343D” manufactured by Ciba Specialty Chemicals Co., Ltd.)
Black: Carbon black pigment (Degussa “Printex 85”)
White: Titanium oxide pigment (Ishihara Sangyo Co., Ltd. “Taipeku CR97”)

The obtained molding resin composition was applied onto a polyethylene terephthalate film that had been subjected to a peeling treatment with a film thickness of 100 μm by using a comma coater so that the dry thickness was 50 μm, and in a gas oven at 120 ° C. And dried and cured for 2 minutes to prepare a sheet.
The release sheet was removed from the obtained sheet, and various tests were performed. Test methods and evaluation methods are as follows. The test results are shown in Table 3. An evaluation value of 3 or more is a practical level.
The test contents evaluated this time show various characteristics required when the obtained sheet is used as a marking film.

  That is, the coatability test evaluates whether a sheet having excellent smoothness, no coating film defects, and excellent appearance characteristics can be obtained.

  The extensibility test evaluates the degree of extensibility of a sheet, but when a sheet is attached as a marking film, the base substrate is not necessarily a flat surface, and is often attached to an uneven adherend. . The extensibility of the sheet is very important for following the unevenness of the adherend. In exterior applications, various base materials are constantly deformed due to heat (sunlight), temperature difference, wind, and the like. In order to evaluate the risk of occurrence of cracks, cracks, etc. of the marking film against such deformation, the stretchability of the sheet is very important.

  The tear strength is an evaluation of the resistance to sheet breakage. When the sheet is pasted as a marking film after being cut into characters and various designs, if the tear strength of the sheet is low, the film is easily broken from the cut edge portion and the construction becomes difficult. Tear strength is a very important performance for workability when applying a marking film.

  The molding process test evaluates whether a sheet can be accurately and accurately cut as a marking film when it is cut into characters and various designs.

  The accelerated weathering test mainly evaluates the degree of change over time such as discoloration, fading, and sheet surface gloss change by sunlight (ultraviolet rays) when it is applied to exterior applications. The smaller the change, the better. In general, the marking film is required to have a weather resistance of 5 years (corresponding to 1000 hours after this test) or more.

  The chemical resistance test evaluates the risk of occurrence of changes in the appearance of the sheet under various environments such as hot water, acid, alkali, and solvent in consideration of various environments.

  Gasoline resistance testing is important when applying marking films mainly for automobile and motorcycle applications. When gasoline adheres to the marking film, whether it is easily peeled off, wrinkles or the like, and how much resistance is important is an important performance in such an application.

  Coating property test: The surface smoothness of the sheet and the presence / absence of pinholes and eyeholes were visually evaluated in five stages (5: excellent, 4: good, 3: acceptable, 2: defective, 1: extremely poor). .

Tensile strength test: A test piece having a width of 1 cm and a length of 5 cm is cut out from a sheet and attached to a tensile tester (“REO METER NRM-2010J-CW” manufactured by Fudo Kogyo Co., Ltd.), with a range of 10 kg and a speed of 30 cm / min. The tensile strength (breaking stress × range / cross-sectional area of the sample) is measured from the maximum load until the specimen is ruptured and the cross-sectional area of the specimen, and is measured in five stages (5: 300 kg / cm ² or more, 4: 200 kg / cm ² or more and less than 300 kg / cm ² , 3: 100 kg / cm ² or more and less than 200 kg / cm ² , 2:50 kg / cm ² or more and less than 100 kg / cm ^{2, and} less than 1:50 kg / cm ² ).

  Extensibility test: The test was performed in the same manner as the tensile strength test, and the elongation rate until the test piece was ruptured was measured. Five stages (0% before stretching: 5: 200% or more, 4: 150%) And less than 200%, 3: 100% to less than 150%, 2: 50% to less than 100%, and less than 1: 50%.

  Tear strength test: A test piece was punched out of the sheet with a JIS K6301 tear B type and attached to a tensile tester ("REO METER NRM-2010J-CW" manufactured by Fudo Kogyo Co., Ltd.) under conditions of a range of 10 kg and a speed of 30 cm / min. The tear strength (breaking stress x range) is measured from the maximum load at the time of pulling and tearing the test piece, and five levels (5: 400 g or more, 4: 300 g or more, less than 400 g, 3: 200 g or more, less than 300 g, 2: 100 g or more, 200 g Less than 1: 100 g).

  Formability test 1: Erichsen test A method according to JIS Z2247, and when the steel ball punch is pressed against the sheet by 10 mm, the change in the appearance of the sheet is visually observed in five stages (5: no change, 4: slightly 3: changed, 2: deteriorated, 1: markedly deteriorated).

  Molding workability test 2: Using a cutting tester ("CM24" manufactured by Roland), the sheet is cut into various pattern shapes, and the cutting accuracy is visually evaluated in five stages (5: excellent, 4: good, 3 : Yes, 2: Bad, 1: Remarkably bad).

  Accelerated weather resistance test: An ultraviolet carbon arc type weather resistance tester (supplied by Suga Test Instruments Co., Ltd.) specified in JIS B7750 is used to perform a test in accordance with JIS K5400 6.17, and changes in appearance after 1000 hours are visually observed. (5: no change, 4: slight change, 3: change, 2: deterioration, 1: significant deterioration).

Chemical resistance test: Visually change the appearance after immersing the sheet in the following chemicals under the following conditions (5: no change, 4: slight change, 3: change, 2: deterioration) , 1: remarkably deteriorated).
[Number: chemicals and evaluation conditions]
1: Immersion in boiling water at 98 ° C. for 5 minutes 2: Isopropyl alcohol Immerse for 1 hour under standard conditions 3: Xylene Immerse for 1 hour under standard conditions 4: Gasoline Immerse for 1 hour under standard conditions 5: 5% saline solution Standard Soaked for 240 hours under conditions 6: 5% aqueous sulfuric acid solution Soaked for 7 hours under standard conditions 7: 5% aqueous sodium hydroxide solution soaked for 7 hours under standard conditions

[Sheet-like cured product with adhesive layer]
Adhesive [mixture of two-component curable acrylic adhesive / curing agent = 100 / 8.7 (weight ratio)] on a 100 μm-thick peelable sheet (“TSM-110K” manufactured by Kite Chemical Co., Ltd.) Then, it was coated using a comma coater, heated in a gas oven at 80 ° C. for 2 minutes, dried and cured, and a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer thickness of about 25 μm was produced.
The pressure-sensitive adhesive layer of the produced pressure-sensitive adhesive sheet and the sheet-like cured product obtained above were bonded together to obtain a sheet-like cured product with a pressure-sensitive adhesive layer.

  Gasoline resistance test: The obtained sheet-like cured product with a pressure-sensitive adhesive layer was cut out to 5.0 cm × 5.0 cm, the peelable sheet was peeled off, and attached to an aluminum plate washed with isopropyl alcohol. Visual change of appearance after immersion in gasoline at 23 ° C for 4 hours (5: no change, 4: slight change, 3: change, 2: deterioration, 1: significant deterioration) evaluated.

(Comparative Examples 7-9)
A soft polyvinyl chloride sheet (Comparative Example 7) having a film thickness of 50 μm, a polyethylene terephthalate sheet (Comparative Example 8) having a film thickness of 60 μm, and a polypropylene sheet (Comparative Example 9) having a film thickness of 60 μm were tested in the same manner as in Example 1. It was. The test results are shown in Table 3.

As is apparent from the test results in Table 3, the sheet or pressure-sensitive adhesive sheet according to the present invention has a performance equivalent to or better than that of a soft polyvinyl chloride sheet with respect to various coating properties required as a marking film, and weather resistance. It showed superior characteristics in gender. In addition, the sheet according to the present invention is a chlorine-free resin and is composed of a resin composition that does not contain a plasticizer, and when used for various decorations, displays, and packaging, it is a very useful sheet and pressure-sensitive adhesive sheet, A molded body is provided.

Claims (10)

Molding comprising an acrylic copolymer (A) having a weight average molecular weight of 5,000 to 500,000, a polyisocyanate compound (B), and a compound (C) having a number average molecular weight of 250 to 10,000. A resin composition for
The acrylic copolymer (A) is obtained by copolymerizing a (meth) acrylic monomer having an isocyanate group, a (meth) acrylic monomer having a hydroxyl group, and another monomer,
The molding resin composition, wherein the compound (C) is a compound selected from the group consisting of polycarbonate, polyester and polybutadiene.   The acrylic copolymer (A) is a copolymer of at least 1 to 10% by weight of a (meth) acrylic monomer having an isocyanate group and 1 to 10% by weight of a (meth) acrylic monomer having a hydroxyl group. The resin composition for molding according to claim 1, wherein   The polyisocyanate compound (B) is contained in an amount of 10 to 50 parts by weight and the compound (C) is contained in an amount of 10 to 100 parts by weight with respect to 100 parts by weight of the acrylic copolymer (A). The resin composition for molding as described. 10 to 100 mol% of the functional group of the compound (D) is reacted with respect to a total of 100 mol% of the isocyanate groups of the acrylic copolymer (A) and the polyisocyanate compound (B),
The compound (D) is a compound selected from the group consisting of an oxime compound, a lactam compound, a phenol compound, an active methylene compound, a heterocyclic compound, and an amino compound. Molding resin composition. Furthermore, a coloring agent is included, The resin composition for shaping | molding in any one of Claims 1-4 characterized by the above-mentioned. 1-10% by weight of an (meth) acrylic monomer having an isocyanate group, 1-10% by weight of a (meth) acrylic monomer having a hydroxyl group, and other monomers are copolymerized to obtain a weight average. Step (1) for obtaining an acrylic copolymer (A) having a molecular weight of 5,000 to 500,000,
A step of obtaining an acrylic copolymer (A-2) by reacting 10 to 100 mol% of the functional group of the compound (D) with respect to 100 mol% of the isocyanate group of the obtained acrylic copolymer (A) ( 2),
Step (3) of obtaining an isocyanate compound (B-2) by reacting 10 to 100 mol% of the functional group of the compound (D) with respect to 100 mol% of the isocyanate group of the polyisocyanate compound (B),
10 to 50 parts by weight of the isocyanate compound (B-2) and 10 to 100 parts by weight of the compound (C) are mixed with 100 parts by weight of the obtained acrylic copolymer (A-2) and stirred. A method for producing a molding resin composition comprising the step (4) of obtaining a resin composition at
The compound (C) is a compound selected from the group consisting of polycarbonate, polyester and polybutadiene,
The method for producing a molding resin composition, wherein the compound (D) is a compound selected from the group consisting of an oxime compound, a lactam compound, a phenol compound, an active methylene compound, a heterocyclic compound and an amino compound.   7. The method for producing a molding resin composition according to claim 6, further comprising blending a colorant in the step (4).   A sheet formed by molding the molding resin composition according to any one of claims 1 to 5, or the molding resin composition obtained by the production method according to claim 6 or 7. A pressure-sensitive adhesive sheet comprising the sheet according to claim 8 and a pressure-sensitive adhesive layer. A molded article formed by molding the sheet according to claim 8 or the adhesive sheet according to claim 9.