JP6100583B2 - Photocurable solventless composition and method for producing the same - Google Patents

Description

  The present invention is a photocurable solventless composition that provides a pressure-sensitive adhesive film and a pressure-sensitive adhesive layer that can be suitably used for foamed base materials such as foamed urethane and foamed rubber, which are difficult to adhere, and olefin base materials such as polypropylene (PP). The present invention relates to a product and a manufacturing method thereof.

  Acrylic adhesive materials are widely used because they are superior in adhesive performance such as adhesive strength and cohesive strength, weather resistance, heat resistance, and solvent resistance compared to other materials such as silicone. It is used. Acrylic adhesive materials are used by adding a crosslinking agent, tackifier, anti-aging agent, etc. as necessary to the acrylic resin as the main agent, and obtained by solution polymerization using an organic solvent as a medium. A solvent type mainly composed of a solution is the mainstream. From the viewpoint of environmental considerations such as VOC (emission solvent regulations) in recent years, some water-based types based on acrylic resin solutions have been put into practical use by emulsion polymerization using water as a medium. In addition, the amount of energy used for volatilizing water is larger than that of the organic solvent system, and there is also a problem of adhesive performance such as poor water resistance compared to the organic solvent type due to the influence of the emulsifier contained in the main agent. In order to solve these problems comprehensively, a solventless type material has been proposed, and a technique for forming an adhesive film by curing with an active energy ray such as ultraviolet rays has been proposed.

  Patent Document 1 proposes a production method in which a pressure-sensitive adhesive film is obtained by irradiating a mixture of acrylic, methacrylic and vinyl monomers and a polyfunctional monomer in the presence of a photopolymerization initiator and a chain transfer agent. In this method, the reaction rate is slowed down by reducing the light irradiation intensity, etc., and a high cohesive film cannot be obtained unless a high molecular weight resin is obtained. It was a technology that was difficult to say.

  Patent Document 2 discloses a solvent-free pressure-sensitive adhesive composition mainly composed of a polymerizable polymer having a molecular weight of 1000 to 50000 in which an olefinically unsaturated bond is introduced into a side chain of a copolymer of an acrylic monomer and a vinyl monomer having a polar group. Things have been proposed. Compared with the technique such as Patent Document 1 by using a polymerizable polymer, it is a technique that enables a curing reaction without slowing the reaction rate, but a hard adhesive film because the molecular weight of the main resin is small. As a result, transfer defects are likely to occur, particularly when a transfer substrate is applied to a substrate having poor wettability such as a foam substrate. Although this problem can be alleviated by reducing the amount of olefinically unsaturated bonds, there is still a problem that cohesive strength is insufficient due to the low molecular weight of the main resin and the adhesive properties such as holding power are impaired. .

  From such a current situation, while exhibiting good transfer sticking performance and adhesive physical properties not only for general plastics and metals, but also for foaming base materials and polypropylene base materials that are difficult to adhere, in actual production lines Therefore, there has been a demand for a photo-curing material that achieves both higher line speed and energy saving.

  By the way, since the solvent-free acrylic resin material does not contain a solvent in the produced polymer, it does not require an operation of removing the solvent by separation or volatilization, and it is an emulsifier that tends to cause deterioration in properties such as water resistance. Since it does not contain such a component, it can be said that it is a suitable material particularly for a material to be photocured. However, in the polymerization reaction of acrylic resins, heat generation during polymerization is generally large, and as the polymerization proceeds, the viscosity increases, so industrially solution polymerization, emulsion polymerization, suspension polymerization, etc. using water or an organic solvent as a medium. In many cases, it is produced by a method in which heat removal is relatively easy. A method of forming a polymerizable polymer by solution polymerization as in Patent Document 2 and then using it as a main component of a solventless composition by removing the solvent has been proposed, but an acrylic resin manufactured in the form of an organic solvent solution It takes a lot of energy and effort to remove only the acrylic resin from the organic solvent. At the same time, the yield is drastically reduced, which is not a satisfactory method from the viewpoint of material productivity.

  As a method for obtaining a solvent-free composition, it can be said that solvent-free polymerization containing no solvent from the raw material stage is the most desirable reaction form. However, solvent-free polymerization cannot be expected to have a dilution effect with a solvent or plasticizer, and it is difficult to control the polymerization reaction rate, so it is extremely difficult to control the heat of polymerization reaction, and the runaway of the polymerization reaction is likely to occur. . The reaction runaway is a very dangerous state with a rapid exothermic heat and a viscosity increase because the reaction cannot be controlled, and it becomes a serious problem particularly when industrially realized.

  The following techniques have been proposed as production methods for obtaining conventional solventless compositions.

  The technique proposed in Patent Document 3 is to obtain a pressure-sensitive adhesive composition comprising a partially polymerized monomer having a polymerizable unsaturated bond mainly composed of an acrylic acid alkyl ester, a crosslinking agent, and a photopolymerization initiator. This is a technique of obtaining a pure acrylic resin mixture containing no solvent and plasticizer by partial polymerization with a solvent-free composition. For the above reaction exothermic problem, the 10-hour half-life temperature and the amount of polymerization initiator are defined, but after the reaction starts, the self-heating of the reaction system due to consumption of the polymerization initiator is utilized. From the point of view of the technique of polymerizing by reaching 100 to 140 ° C., the reaction rate during the polymerization is not controlled, and the calorific value that will increase in the process of increasing the scale industrially is increased. It is inferred that this is not a technique that can be adjusted or suppressed.

  On the other hand, in the technique proposed in Patent Document 4, 2,4-diphenyl-4-methyl-1-pentene (= α-methylstyrene dimer), an ethylenic polymer having a methacryloyl group in the presence of a radical polymerization initiator. A method for producing a block copolymer by radical polymerization of a saturated compound (= acrylic monomer) has been proposed. In the technique proposed in Patent Document 4, living radical polymerization is realized using 2,4-diphenyl-4-methyl-1-pentene (= α-methylstyrene dimer) as an addition-cleavage chain transfer agent. However, no consideration is given to stirring and heat removal of polymerization heat, which are more important in manufacturing acrylic resins and are fundamental safety issues, and solutions that are easy to stir and remove heat. It is assumed that it is necessary to produce by polymerization. From such a viewpoint, in the method proposed in Patent Document 4, even if a copolymer is produced, it is necessary to remove the organic solvent from the acrylic resin produced in the form of a solution of the organic solvent. As with, productivity remains a problem.

  As described above, there has been a demand for a satisfactory technique for obtaining a solvent-free composition in a safe and simple manner in consideration of industrial productivity.

JP-A-3-84011 JP-A-57-109873 JP 2001-181589 A JP 2000-169531 A

  The present invention provides a photocurable solventless composition that achieves both the manifestation of adhesive performance on various substrates including difficult-to-adhere substrates, which has been difficult with the prior art, as well as speeding up the production process and saving energy. An object of the present invention is to provide a production method that can solve the safety that has been difficult on a conventional industrial scale and can be easily produced.

  As a result of studying to obtain an adhesive material as described above, a mixture of a polymerizable polymer having a specific molecular weight, a degree of dispersion and a polymerizable double bond, a chlorinated polypropylene resin, and a photopolymerization initiator is photocured to produce an adhesive film. In addition to polyethylene terephthalate (PET) base material, stainless steel (SUS) and other metal base materials, foam transfer base materials such as foam rubber and olefin resin base materials have a good balance of transfer paste and adhesiveness. It has been found that the adhesive film can be obtained in a very short time because it has sufficient curability when irradiated with light having a low intensity and a low amount of light.

（式中、Ｒ¹は水素原子またはメチル基、ｎは０〜６の整数を表し、複数のｎが混在してもよい。） The photocurable solventless composition of the present invention comprises a solvent, a solventless polymerizable copolymer composition (A) containing no plasticizer, chlorinated polypropylene (B), and a polymerization initiator that absorbs ultraviolet rays and generates radicals. (C) a photocurable solventless composition, wherein the solventless polymerizable copolymer composition (A) is a (meth) acrylic acid ester monomer having an alkyl group having 4 or more carbon atoms (A), a (meth) acrylate ester comprising a polymerizable monomer (b) having a nitrogen atom in the molecule, and a (meth) acrylate monomer (c) represented by the following general formula (1) A mixture of the copolymer and the monomers (a), (b), and (c), wherein the (meth) acrylic acid ester copolymer has a weight average molecular weight (Mw) of 200 to 400,000, and the weight average molecular weight ( Mw) and the number average molecular weight (Mn) ratio (Mw / Mn) The dispersity is 2.0 to 5.0, and the side chain has 3 to 10 mol of polymerizable double bonds per mol of copolymer molecules, and the blending amount of the chlorinated polypropylene (B) is 1 to 8% by weight. The blending amount of the polymerization initiator (C) is 0.5 to 8% by weight .

(In the formula, R ¹ represents a hydrogen atom or a methyl group, n represents an integer of 0 to 6, and a plurality of n may be mixed.)

  Furthermore, with respect to heat generation control, which is a problem when the photocurable solventless composition is obtained by solventless polymerization, it is not radical polymerization, which is generally difficult to control the reaction, but living polymerization that can control the reaction rate. It has been found that the problem can be solved by applying a photocatalyst, and has also come up with a method for producing a photocurable solventless composition industrially and safely.

  The method for producing the photocurable solventless composition of the present invention is a method for producing the photocurable solventless composition described above, and is a (meth) acrylic acid ester monomer having an alkyl group having 4 or more carbon atoms. (A) A monomer mixture comprising a polymerizable monomer (b) having a nitrogen atom in the molecule and a (meth) acrylic acid ester monomer (c) represented by the general formula (1) is prepared. In the total amount of the monomer mixture, the (meth) acrylic acid ester copolymer is copolymerized so that the conversion is 20 to 60% by weight. The curable copolymer composition (A) is prepared, and a chlorinated polypropylene (B) and a polymerization initiator (C) that absorbs ultraviolet rays to generate radicals are dissolved and mixed therein.

  The photocurable solventless composition of the present invention exhibits a good balance of peel strength and holding power when used as an adhesive film material, and is a foamed rubber that is particularly difficult to adhere to in addition to PET and metal substrates. In a very short time, it has a good balance of adhesiveness and adhesiveness to foamed substrates such as polypropylene and olefin resin substrates such as polypropylene, and has sufficient curability when irradiated with light of low intensity and low light intensity. An adhesive film can be obtained.

  Further, in obtaining the photocurable solventless composition of the present invention, in batch polymerization with a solventless composition not containing a solvent and a plasticizer, avoiding and controlling the process leading to rapid polymerization reaction and runaway reaction. In addition, a production method that solves safety and disaster prevention problems including stirring and heat removal can be obtained.

  Hereinafter, the present invention will be described in more detail.

  The photocurable solventless composition of the present invention comprises a solventless polymerizable copolymer composition (A), a chlorinated polypropylene (B), and a polymerization initiator (C) that absorbs ultraviolet rays and generates radicals.

（式中、Ｒ¹は水素原子またはメチル基、ｎは０〜６の整数であり、単一でも複数のｎが混在してもよい。） Solvent-free polymerizable copolymer composition (A) is a solvent-free composition containing no solvent and plasticizer, and a (meth) acrylic acid ester monomer (a) having an alkyl group having 4 or more carbon atoms, A (meth) acrylic acid ester copolymer comprising a polymerizable monomer (b) having a nitrogen atom in the molecule and a (meth) acrylic acid ester monomer (c) represented by the following general formula (1): It is composed of a mixture of the monomers (a), (b) and (c).

(In the formula, R ¹ is a hydrogen atom or a methyl group, n is an integer of 0 to 6, and a single or a plurality of n may be mixed.)

  In the present invention, as the (meth) acrylic acid ester monomer (a) having an alkyl group having 4 or more carbon atoms, for example, n-butyl acrylate, isobutyl acrylate, tertiary butyl acrylate, cyclohexyl acrylate, (Meth) acrylic acid alkyl esters such as 2-ethylhexyl acrylate, lauryl acrylate, n-butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, etc. The body can be exemplified. These monomers may be used alone or in a mixture of two or more. Among these, n-butyl acrylate and 2-ethylhexyl acrylate are preferable in consideration of availability, polymerizability, characteristics of the obtained polymer, and the like.

  The (meth) acrylic acid ester monomer (a) having an alkyl group having 4 or more carbon atoms is preferably 60 to 95% by weight, more preferably 70 to 95% of the solventless polymerizable copolymer composition (A). 95% by weight, more preferably 80 to 95% by weight may be used. When the ratio of the (meth) acrylic acid ester monomer (a) is less than 60% by weight, the glass transition temperature tends to increase, and the adhesiveness to the foamed substrate tends to be impaired, and is more than 95% by weight. The cohesive force is insufficient and the adhesive performance such as holding power tends to be impaired.

  In the present invention, the polymerizable monomer (b) having a nitrogen atom in the molecule includes N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, 4-methacryloyloxy-2,2, 6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine, 3-methacryloyloxyethylethyleneurea, N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, acryloylmorpholine, Methacryloylmorpholine, acrylamide, N, N-dimethylacrylamide, ethylacrylamide, isopropylacrylamide, N-methylolacrylamide, 2-hydroxyethylacrylamide, N, N-dimethylaminopropylacrylamide, N, N Diethylaminopropylacrylamide, methacrylamide, N, N-dimethylmethacrylamide, ethylmethacrylamide, isopropylmethacrylamide, N-methylolmethacrylamide, 2-hydroxyethylmethacrylamide, N, N-dimethylaminopropylmethacrylamide, N, N- Examples include diethylaminopropyl methacrylamide, N-phenylmaleimide, N-cyclohexylmaleimide and the like. These monomers may be used alone or in a mixture of two or more. Among these, N-vinylpyrrolidone and / or 2-dimethylaminoethyl methacrylate are preferred in consideration of availability, polymerizability, characteristics of the obtained polymer, and the like.

  The polymerizable monomer (b) having a nitrogen atom in the molecule of the present invention is preferably 3 to 30% by weight, more preferably 5 to 25% by weight of the solventless polymerizable copolymer composition (A). More preferably 5 to 20% by weight is used. When the ratio of the polymerizable monomer (b) having a nitrogen atom in the molecule is less than 3% by weight, the cohesive force is insufficient, and the adhesive performance such as holding power tends to be impaired, and is 30% by weight or more. And the glass transition temperature rises, and the adhesiveness to the foamed substrate tends to be impaired.

  In the present invention, examples of the (meth) acrylic acid ester monomer (c) represented by the general formula (1) include acrylic acid, methacrylic acid, and 2-carboxyethyl acrylate oligomer. These (meth) acrylic acid ester monomers may be used alone or in a mixture of two or more. In terms of availability, acrylic acid and methacrylic acid are preferable, and 2-carboxyethyl acrylate oligomer is preferable in consideration of the reactivity of subsequent modification.

  The (meth) acrylic acid ester monomer (c) represented by the general formula (1) is preferably 1 to 30% by weight, more preferably 3 to 3% by weight of the solventless polymerizable copolymer composition (A). It is recommended to use 25% by weight, more preferably 5 to 20% by weight. When the ratio of the (meth) acrylic acid ester monomer (c) is less than 1% by weight, the cohesive force is insufficient, and the adhesive performance such as holding power tends to be impaired. The temperature rises and the adhesiveness to the foamed substrate tends to be impaired.

  In the present invention, monomers other than those described above can be used as necessary. 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono ( Hydroxyl group-containing monomers such as (meth) acrylate and polytetramethylene glycol mono (meth) acrylate, dicyclopentanyloxyethyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate Acrylic monomers derived from dicyclopentadiene such as allyl acrylate, allyl methacrylate, benzyl methacrylate, meta (Meth) acrylic acid ester monomers such as acrylic acid tetrahydrofurfuryl can be used. In the present invention, these monomers may be used alone or in a mixture of two or more.

  The (meth) acrylic acid ester monomer (a) having an alkyl group having 4 or more carbon atoms, contained in the solvent-free polymerizable copolymer composition (A) of the present invention, and having a nitrogen atom in the molecule The (meth) acrylic acid ester copolymer composed of the monomer (b) and the (meth) acrylic acid ester monomer (c) represented by the general formula (1) has a weight average molecular weight (Mw) of 20 to 20%. The dispersity represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2.0,000, preferably 200 to 350,000, more preferably 200 to 300,000. It is -5.0, Preferably it is 2.0-4.0, More preferably, it is 2.0-3.5. If the weight average molecular weight (Mw) is less than 200,000, the cohesive force tends to be insufficient, and the adhesive performance such as holding power tends to be impaired. If it exceeds 400,000, the resulting solventless polymerizable copolymer composition Viscosity increases and coating tends to be difficult. If the dispersity represented by Mw / Mn is less than 2.0, tackiness (initial tackiness) tends to be impaired, and if it exceeds 5.0, the cohesive force is lowered and the adhesive performance such as holding power is reduced. There is a tendency to lose. In the present invention, the weight average molecular weight (Mw) and number average molecular weight (Mn) are measured by using gel permeation chromatography (GPC) and calibrating with polymethyl methacrylate as a standard.

  The (meth) acrylic acid ester copolymer contained in the solventless polymerizable copolymer composition (A) in the present invention has a polymerizable double bond in the copolymer side chain. In this case, polymerization reactivity can also be imparted to the copolymer part, and it can be cured with less energy during the curing reaction of the solventless polymerizable copolymer composition (A). The adhesion performance can be improved by increasing the cohesive force.

  The modification method for introducing a polymerizable double bond into the side chain of the copolymer is not particularly limited. For example, a monomer having a functional group such as a hydroxyl group, an epoxy group, or a carboxyl group is co-polymerized in the copolymer. After polymerization, a general method of introducing a functional group capable of reacting with these functional groups and a compound having a polymerizable double bond into a copolymer side chain by addition reaction can be used. In the present invention, a compound that reacts with the carboxyl group introduced into the side chain of the copolymer by copolymerizing the (meth) acrylic acid ester monomer (c) represented by the general formula (1) is used. It is preferable to add, and as this compound, glycidyl acrylate or glycidyl methacrylate having an epoxy group can be suitably used from the viewpoint of availability and cost.

  The (meth) acrylic acid ester copolymer contained in the solvent-free polymerizable copolymer composition (A) in the present invention preferably has 3 to 10 mol of polymerizable double bonds per mol of copolymer molecules in the side chain. 4-10 mol, more preferably 5-10 mol. When the number of moles of the polymerizable double bond per mole of the copolymer molecule is less than 3 mol, there is a tendency that sufficient curability cannot be obtained when cured, and when it exceeds 10 mol, Adhesive performance tends to be impaired. Here, the mol number of the polymer is obtained by dividing the weight of the obtained polymer by the weight average molecular weight, and the mol number of the polymerizable double bond is the mol number of the reacted epoxy group-containing compound.

  In the present invention, the method for producing a (meth) acrylic acid ester copolymer contained in the solvent-free polymerizable copolymer composition (A) includes a weight average molecular weight (Mw), a degree of dispersion (Mw / Mn), and a side chain. It is not particularly limited as long as the amount of the polymerizable double bond in the above satisfies the above range, but it is obtained by bulk polymerization using living radical polymerization in consideration of obtaining a solvent-free composition safely and easily. Is preferred. Specifically, a (meth) acrylic acid ester monomer (a) having an alkyl group having 4 or more carbon atoms, a polymerizable monomer (b) having a nitrogen atom in the molecule, and the general formula (1) The total amount of the mixture containing the (meth) acrylic acid ester monomer (c) is preferably 20 to 60% by weight, more preferably 30 to 55% by weight, still more preferably 30 to 50% by weight. A copolymer can be obtained by bulk polymerization to obtain a solvent-free polymerizable copolymer composition (A). When the ratio of converting the mixture of monomers (a), (b), and (c) to a polymer is less than 20% by weight, the adhesive and curing functions of the polymer part tend to be difficult to develop when the adhesive film is formed. If it exceeds 60% by weight, the viscosity of the resulting solventless polymerizable copolymer composition tends to increase, and coating tends to be difficult.

  In the above production method of the present invention, it is preferable to apply living radical polymerization in which the reaction rate can be controlled for the purpose of controlling heat generation, which has been difficult with bulk polymerization. Examples of living radical polymerization include unstable radical polymerization, atom transfer polymerization, and addition-open chain transfer polymerization, but addition-cleavage chain transfer polymerization is particularly suitable because of the availability and cost of the catalyst used. it can.

  In the living radical bulk polymerization for obtaining the solvent-free polymerizable copolymer composition (A) in the present invention, the addition open-chain chain transfer agent (d) is a polymerization initiator having a 10-hour half-life temperature of 30 to 50 ° C. It is preferable to manufacture by the method of using 2 mol times or more of (e), performing a 1st polymerization reaction at 50 degrees C or less, and then performing a 2nd polymerization reaction at 60-100 degreeC. Thereby, a (meth) acrylic acid ester copolymer having a molecular weight and a dispersion degree satisfying the above ranges can be obtained.

Examples of the addition open-chain transfer agent (d) include α-methylstyrene dimer, 2-cyano-2-propylbenzodithionate, cyanomethyldodecyltrithiocarbonate, bis (thiobenzoyl) disulfide and the like. Among these, α-methylstyrene dimer represented by the following chemical formula (2), that is, 2,4-diphenyl-4-methyl-1-pentene, is easily available and inexpensive, and thus can be particularly preferably used.

  In the production method of the present invention, the 10-hour half-life temperature of the polymerization initiator (e) is preferably 30 to 50 ° C, more preferably 30 to 45 ° C, still more preferably 30 to 40 ° C, and particularly preferably 30 to 30 ° C. It is good at 35 degreeC. When the 10-hour half-life temperature of the polymerization initiator (e) is less than 30 ° C., a large exotherm may occur temporarily immediately after the polymerization initiator is charged. The 10-hour half-life temperature of the polymerization initiator (e) When the temperature is over 50 ° C, sudden heat generation immediately after the initiator is charged can be suppressed, but the reaction does not proceed, the reaction time is long, and a large heat generation may occur temporarily when the polymerization temperature is raised thereafter. There is a tendency not to perform bulk polymerization. Here, in the method for producing an acrylic ester copolymer of the present invention, the 10-hour half-life temperature refers to a temperature at which the concentration of the polymerization initiator is reduced by half in 10 hours, and is a value published by the manufacturer of the polymerization initiator. It was adopted.

  As the polymerization initiator (e) having a 10-hour half-life temperature of 30 to 50 ° C. used in the production method of the present invention, for example, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (“V-70” manufactured by Wako Pure Chemical Industries, Ltd.) (10-hour half-life temperature 30 ° C.), diisobutyl peroxide (“Paroyl IB” manufactured by NOF Corporation) (10-hour half-life temperature 33 ° C.), cumyl peroxyneo Decanoate (Nippon "Park Mill ND") (10-hour half-life temperature 37 ° C), Dinormalpropyl peroxydicarbonate (Nippon "Perroyl NPP") (10-hour half-life temperature 40 ° C), Diisopropyl peroxydicarbonate (“Paroyl IPP” manufactured by NOF Corporation) (10 hour half-life temperature 41 ° C.), disecondary butyl peroxydicarbonate (“PARO manufactured by NOF Corporation”) IL SBP ") (10-hour half-life temperature 41 ° C), 1,1,3,3-tetramethylbutyl peroxyneodecanoate (" Perocta ND "manufactured by NOF Corporation) (10-hour half-life temperature 41 ° C) , Di (4-tertiarybutylcyclohexyl) peroxydicarbonate (“Perroyl TCP” manufactured by NOF Corporation) (10 hour half-life temperature 41 ° C.), 1-cyclohexyl-1-methylethylperoxyneodecanoate (Japan) “Percyclo ND” (manufactured by Oil Co., Ltd.) (10-hour half-life temperature 41 ° C.), di (2-ethoxyethyl) peroxydicarbonate (“Parroyl EEP” manufactured by NOF Corporation) (10-hour half-life temperature 43 ° C.), di (2-Ethylhexyl) peroxydicarbonate (“PAROIL OPP” manufactured by NOF Corporation) (10 hours half-life temperature 44 ° C.), tertiary hexyl peroxyneode Canoate (“NOF Corporation“ Perhexyl ND ”) (10-hour half-life temperature 45 ° C.), dimethoxybutyl peroxydicarbonate (NOF“ Perroyl NBP ”) (10-hour half-life temperature 46 ° C.), tertiary butyl Examples thereof include peroxyneodecanoate (“Perbutyl ND” manufactured by NOF Corporation) (10-hour half-life temperature: 46 ° C.). In the production method of the present invention, the polymerization initiator may be used alone or in a mixture of two or more. Among these, in particular, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (“V-70” manufactured by Wako Pure Chemical Industries, Ltd.) (10 hour half-life temperature 30 ° C.), diisobutyl Peroxide ("NOVA" "Parroyl IB") (10-hour half-life temperature 33 ° C), cumyl peroxyneodecanoate (NOF "Park Mill ND") (10-hour half-life temperature 37 ° C), The polymerization temperature is easily controlled, the polymerization rate is high, and the production time tends to be shortened.

  In the production method of the present invention, the addition open-chain chain transfer agent (d) is preferably 2 mol times or more, more preferably 2 to 50 mol times the polymerization initiator (e) having a 10-hour half-life temperature of 30 to 50 ° C. More preferably, when used in an amount of 2 to 35 mol times, particularly preferably 2 to 20 mol times, the polymerization rate is controlled appropriately, the amount of heat generated during production becomes easy, and the production of the acrylate copolymer is safe. Therefore, safe bulk polymerization is possible. When the ratio of the addition open chain transfer agent (d) to the polymerization initiator (e) is less than 2 mol, rapid and intense heat generation occurs during the production of the acrylic ester copolymer of the acrylic monomer, and the reaction runaway occurs. In the case of more than 50 mol, bulk polymerization can be carried out safely, but the polymerization rate is slow, the production time is long, and there are few industrial advantages.

  In the production method of the present invention, the first polymerization reaction is preferably performed at 50 ° C. or lower, more preferably at 25 ° C. to 50 ° C., and then the second polymerization reaction is preferably performed at 60 to 100 ° C., more preferably. It is good to carry out at 60-90 degreeC, More preferably, it is 60-80. By such a polymerization method, a polymerization intermediate is obtained by the first polymerization reaction, and then living polymerization is carried out by the second polymerization reaction, thereby obtaining a copolymer having a plurality of peaks. Not only the molecular weight (Mw) but also the degree of dispersion (Mw / Mn) that tends to be small in ordinary living polymerization can be obtained in the range of 2.0 to 5.0.

  In order to introduce a polymerizable double bond into the side chain of the (meth) acrylic acid ester copolymer contained in the solvent-free polymerizable copolymer composition (A) in the present invention, a (meth) acrylic acid ester It is preferable to add glycidyl acrylate or glycidyl methacrylate to the carboxyl group introduced into the copolymer side chain by copolymerizing the monomer (c).

  In the photocurable unnecessary composition of the present invention, the amount of the solvent-free polymerizable copolymer composition (A) is preferably 80 to 99.3% by weight, more preferably in the photocurable unnecessary composition. Is 85 to 95% by weight, more preferably 90 to 95% by weight. When the blending amount of the solventless polymerizable copolymer composition (A) is less than 80% by weight, the effects of curability and pressure-sensitive adhesive properties tend to decrease. If the blending amount of the solventless polymerizable copolymer composition (A) exceeds 99.3% by weight, the effects of other additives will tend not to be sufficiently exhibited although the effects of curability and adhesive properties can be obtained.

  The photocurable unnecessary composition of the present invention contains chlorinated polypropylene (B). By containing the chlorinated polypropylene (B), it is possible to express good adhesiveness to a polypropylene substrate that is usually difficult to adhere.

  As chlorinated polypropylene (B), commercially available products such as HARDLEN (manufactured by Toyobo Co., Ltd.) and Sparklon (manufactured by Nippon Paper Chemicals Co., Ltd.) can be used. However, when using a pellet type that is not diluted with a solvent, Since the material does not contain a solvent, it can be suitably used. Examples of the hard len series include 13-LP, 13-LLP, 14LWP, 15-LLP, 16-LP, DX-523P, DX-526P, DX-530P and the like. Since these differences are different in molecular weight and degree of chlorination, a grade of chlorination degree suitable for solubility and compatibility can be arbitrarily selected. In the present invention, DX-523P, DX-526P, and DX-530P can be suitably used from the viewpoints of solubility and compatibility.

In the present invention, the amount of chlorinated polypropylene (B) is photocurable solventless composition, 1-8% by weight, good Mashiku is you 2-6 wt%. When the blending amount of chlorinated polypropylene (B) is less than 1 % by weight, the adhesion to the polypropylene base material is insufficiently improved, and when it exceeds 8 % by weight, the viscosity of the photocurable unnecessary composition increases. Tend to be difficult.

  The mixing method of the chlorinated polypropylene (B) is not particularly limited, but it is preferable to dissolve and mix in the monomer in consideration of solubility. You may melt | dissolve in the monomer mixture before block polymerization, and you may mix in the solventless polymerizable copolymer composition (A) obtained by reaction.

  The photocurable unnecessary composition of the present invention contains a polymerization initiator (C) that absorbs ultraviolet rays and generates radicals. By containing a polymerization initiator (C) that absorbs ultraviolet rays and generates radicals, a curing reaction can be initiated by irradiation with ultraviolet rays, and a cured film can be obtained.

  Examples of the polymerization initiator (C) that absorbs ultraviolet rays and generates radicals according to the present invention include benzophenone, 2,2'-dimethoxy-1,2-diphenylethane-1-one, and 1-hydroxy-cyclohexyl-phenyl-ketone. 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-hydroxy-1- (4- (4- (2-hydroxy-2-methyl-propionyl) -benzyl) phenyl) -2- Methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butanone-1-one, 2-dimethylamino-2- (4-methyl-benzyl) -1- ( -Morpholin-4-yl-phenyl) -butan-1-one, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. it can. The polymerization initiator (C) that absorbs ultraviolet rays and generates radicals according to the present invention can be arbitrarily selected according to the wavelength of ultraviolet rays irradiated during curing and the cured film thickness. Benzophenone, 2,2'-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide for thick film curing 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide can be preferably used.

The amount of the polymerization initiator that generates ultraviolet absorbing radical (C) of the present invention photocurable solventless composition, 0.5-8 wt%, good Mashiku is to use 1-6% by weight . The blending amount of the polymerization initiator (C) is 0. If it is less than 5 % by weight, the curing conversion rate is lowered and the film odor tends to deteriorate due to the remaining unreacted monomer. If it exceeds 8 % by weight, the solubility becomes poor and the cured film becomes cloudy. There is a tendency for tsutsu and yellowing to occur.

  The method for mixing the polymerization initiator (C) that absorbs ultraviolet rays and generates radicals according to the present invention is not particularly limited, but it is preferable to dissolve and mix in a monomer in consideration of solubility. After mixing, since a curing reaction occurs due to ultraviolet rays, it is necessary to shield from light. Therefore, the mixture should be finally mixed with the solvent-free polymerizable copolymer composition (A) and chlorinated polypropylene (B) obtained by the reaction. Is preferred.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example and a comparative example, this invention is not limited to a following example. In addition, the analytical value and characteristic of the (meth) acrylic acid ester copolymer were measured by the following method.

1) Polymerization state (mainly exothermic state)
The exothermic state when polymerizing the (meth) acrylic acid ester copolymer was determined according to the following criteria.
○ (Accepted): When the set temperature ± 2 ° C. can be maintained in all reaction steps without sudden exotherm.
X (failed): When there is an exotherm exceeding 3 ° C. in 10 seconds, or when the set temperature ± 2 ° C. cannot be maintained due to exotherm or endotherm in all reaction steps.

2) Polymer conversion rate (unit:% by weight)
The heating residue (% by weight) was measured according to JIS K5407: 1997, and this was defined as the polymerization rate (% by weight). However, the heating conditions were a temperature of 140 ° C. and a time of 30 minutes.

3) Weight average molecular weight (Mw) and number average molecular weight (Mn)
Using gel permeation chromatography (GPC) “HLC-8220GPC” (tester of Tosoh Corporation), the carrier was measured as tetrahydrofuran, and calibrated using polymethyl methacrylate as the standard, and the number average molecular weight (Mn ) And weight average molecular weight (Mw). The dispersity (Mw / Mn) was determined by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn).

4) Reaction rate of glycidyl (meth) acrylate (unit: wt%)
Using high-performance liquid chromatography (HPLC) (Shimadzu test equipment), distilled water and acetonitrile as eluents, using a reverse-phase column and an ultraviolet detector, the internal standard method (standard material anisole) was used to remain (meta ) Glycidyl acrylate was quantified. Using this value, the reaction rate of glycidyl (meth) acrylate was calculated from the following formula.

5) Number of mols of double bonds per mol of polymer (unit: mol)
It was calculated by the following formula.

6) UV curing method Adhesive material adjusted to a thickness of 60 μm sandwiched between two separate films, using a UV irradiation machine CS30R1-1 (manufactured by GS NIPPON DENCHI) with a high-pressure mercury lamp, irradiation intensity 100 mW / cm ² and cured under conditions of an integrated light quantity of 200 mJ / cm ² .

7) Curing conversion rate (unit:%)
The height of the double bond-derived peak (810 cm ⁻¹ ) was determined for the UV-cured pressure-sensitive adhesive film by FT-IR, and the percentage of the peak height of the pressure-sensitive adhesive material before curing was taken as the curing conversion rate (%).

  It can be judged that the higher the curing conversion rate is, the higher the curability is and the less the residual monomer is, and 97% or more is judged as acceptable.

8) Gel fraction (unit:% by weight)
50 ml of toluene was added to about 0.3 g of the cured film obtained by UV curing, and allowed to stand at 25 ° C. for 5 days. Thereafter, the solution was filtered through a 400 mesh wire mesh, dried at 100 ° C. for 3 hours, and then the weight of the film remaining on the wire mesh was measured. The percentage of the film weight remaining on the wire mesh with respect to the weight before immersion in toluene was defined as the gel fraction.

  As the adhesive material, it indicates that the gel fraction is too low, the curing is insufficient, and when the gel fraction is too high, it indicates that the film is too hard. .

9) Ball tack Measured according to the tack test method (ball rolling method) of JIS Z0237. It can be determined that the larger the number of the ball tack, the higher the tack. In this embodiment, the ball tack is determined to be acceptable when the number is 10 or more.

10) Substrate transfer property One side of a UV-cured cured film sandwiched between separate films is peeled off and brought into contact with a 1 cm thick flexible urethane foam. The thickness of the urethane foam from the urethane foam side is 0.7 cm. A load was applied uniformly so as to be 1 min. Thereafter, when the remaining separate film was peeled by hand, it was determined to be acceptable (O) if the urethane foam and the adhesive layer were adhered, and rejected (X) if the interface peeled.

11) Peel strength (unit: N / 25mm)
Measured according to JIS Z0237: 2000 “90-degree peeling method”. However, a flexible urethane foam having a width of 25 mm was used as the substrate, and a commercially available polypropylene plate (manufactured by Partec Co., Ltd.) was used as the adherend. It can be determined that the higher the peel strength is, the higher the adhesive strength is. In the present invention, it is determined to be acceptable when the peel strength is 6 N / 25 mm or more.

12) Holding power It measured according to JIS Z0237: 2000 "holding power". However, a flexible urethane foam having a width of 25 mm was used as the base material, and a commercially available polypropylene plate (manufactured by Partec Co., Ltd.) was used as the adherend, and the load was 500 g. It was determined that the higher the holding force, the higher the adhesion maintaining force, and when the deviation from the initial sticking position was within 4 mm after 24 hours, it was determined to be acceptable.

<Preparation of solvent-free polymerizable copolymer composition (A)>
[Synthesis Example 1]
In a 2 L four-necked flask having a nitrogen gas inlet tube, a reflux condenser, a stirring device, and a charging port, 830 g of 2-ethylhexyl acrylate, 120 g of N-vinylpyrrolidone, 50 g of acrylic acid, 1 g of α-methylstyrene dimer (polymerization initiator) 6.5 mol times) and stirred while bubbling with nitrogen gas, and the temperature of the mixture was adjusted to 50 ° C. Next, 0.2 g of 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (“V-70” manufactured by Wako Pure Chemical Industries, Ltd., 10 hour half-life temperature 30 ° C.) was added. After reacting for 2 hours while maintaining the temperature at 50 ° C., the temperature is raised to 70 ° C., and when the polymerization conversion becomes about 45% by weight, the supply air in the flask is switched from nitrogen to air and p. -The reaction was stopped by adding 0.5 g of methoxyphenol. Next, 3 g of glycidyl methacrylate and 4 g of N, N′-dimethylbenzylamine were added and reacted at 90 ° C. for 6 hours while bubbling with air to obtain a polymer composition P-1.

  The obtained polymer composition P-1 was not observed to have a rapid exotherm within the entire reaction time, and could be produced without any problem in safety. Polymer composition P-1 had a polymerization conversion rate of 45.0% by weight, a weight average molecular weight (Mw) of 255,000, a dispersity (Mw / Mn) of 2.5, and a double per mole of polymer molecule. The binding amount (mol number) was 5.4 mol.

[Synthesis Example 2]
It was prepared in the same manner as in Synthesis Example 1 except that the charged composition in Synthesis Example 1 was changed to 830 g of 2-ethylhexyl acrylate, 100 g of N-vinylpyrrolidone, and 70 g of acrylic acid, and the polymerization conversion was about 48% by weight. The reaction was stopped at that time. Next, 3 g of glycidyl methacrylate was reacted to obtain a polymer composition P-2.

  The obtained polymer composition P-2 was able to be produced without any problem in safety because no rapid heat generation was observed within the entire reaction time. Polymer composition P-2 has a polymerization conversion rate of 48.2% by weight, a weight average molecular weight (Mw) of 305,000, a dispersity (Mw / Mn) of 2.4, and a double per mol of polymer molecule. The binding amount (mol number) was 6.4 mol.

[Synthesis Example 3]
Using the same apparatus as in Synthesis Example 1, 250 g of 2-ethylhexyl acrylate, 550 g of n-butyl acrylate, 150 g of acrylamide, 50 g of β-CEA (manufactured by Rhodia Nikka), 1 g of α-methylstyrene dimer (polymerization start) The mixture was stirred while bubbling with nitrogen gas, and the temperature of the mixture was adjusted to 50 ° C. Next, 0.2 g of 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) was added. After reacting for 2 hours while maintaining the temperature at 50 ° C., the temperature was raised to 70 ° C., and the reaction was stopped in the same manner as in Synthesis Example 1 when the polymerization conversion reached about 45% by weight. Next, 2.5 g of glycidyl methacrylate was reacted to obtain a polymer composition P-3.

  The obtained polymer composition P-3 was able to be produced without any problem in safety because no rapid heat generation was observed within the entire reaction time. Further, the polymerization conversion rate of the polymer composition P-3 was 46.7% by weight, the weight average molecular weight (Mw) was 259,000, the dispersity (Mw / Mn) was 2.6, and the double per mol of the polymer molecule. The binding amount (mol number) was 4.6 mol.

[Synthesis Example 4]
Using the same apparatus as in Synthesis Example 1, 780 g of 2-ethylhexyl acrylate, 120 g of N-vinylpyrrolidone, 100 g of β-CEA, 1.2 g of α-methylstyrene dimer (7.8 mol times the polymerization initiator) are charged. The mixture was stirred while bubbling with nitrogen gas, and the temperature of the mixture was adjusted to 50 ° C. Next, 0.2 g of 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) was added. After reacting for 2 hours while maintaining the temperature at 50 ° C., the temperature was raised to 70 ° C., and the reaction was stopped in the same manner as in Synthesis Example 1 when the polymerization conversion reached about 40% by weight. Next, 2.0 g of glycidyl methacrylate was reacted to obtain a polymer composition P-4.

  The obtained polymer composition P-4 was able to be produced without any problem in safety because no rapid heat generation was observed within the entire reaction time. In addition, the polymerization conversion rate of the polymer composition P-4 was 41.1% by weight, the weight average molecular weight (Mw) was 230,000, the dispersity (Mw / Mn) was 2.7, and the double per mol of polymer molecule. The binding amount (mol number) was 3.2 mol.

[Synthesis Example 5]
Using the same apparatus as in Synthesis Example 1, 430 g of 2-ethylhexyl acrylate, 430 g of n-butyl acrylate, 80 g of N-vinylpyrrolidone, 60 g of β-CEA, 1 g of α-methylstyrene dimer (6. of polymerization initiator). 5 mol times) was added and stirred while bubbling with nitrogen gas, and the temperature of the mixture was adjusted to 50 ° C. Next, 0.2 g of 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) was added. After reacting for 2 hours while maintaining the temperature at 50 ° C., the temperature was raised to 75 ° C., and the reaction was stopped in the same manner as in Synthesis Example 1 when the polymerization conversion reached about 47% by weight. Next, 2.5 g of glycidyl methacrylate was reacted to obtain a polymer composition P-5.

  The obtained polymer composition P-5 was able to be produced without any problem in safety because no rapid heat generation was observed within the entire reaction time. In addition, the polymerization conversion rate of the polymer composition P-5 was 47.0% by weight, the weight average molecular weight (Mw) was 259,000, the dispersity (Mw / Mn) was 2.3, and the double per mol of the polymer molecule. The binding amount (mol number) was 4.6 mol.

[Synthesis Example 6]
Using the same apparatus as in Synthesis Example 1, 600 g of 2-ethylhexyl acrylate, 300 g of n-butyl acrylate, 70 g of N-vinylpyrrolidone, 30 g of methacrylic acid, 10 g of α-methylstyrene dimer (13.0 mol of polymerization initiator) The mixture was stirred while being bubbled with nitrogen gas, and adjusted to 25 ° C. 1 g of 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) was added and reacted while the temperature was raised to 50 ° C. over 2.5 hours, and then the temperature was raised to 90 ° C. The reaction was stopped in the same manner as in Synthesis Example 1 when the polymerization conversion reached about 50% by weight. Next, 5 g of glycidyl methacrylate was reacted to obtain a polymer composition P-6.

  The obtained polymer composition P-6 was able to be produced without any problem in safety because no rapid heat generation was observed within the entire reaction time. In addition, the polymerization conversion rate of the polymer composition P-6 was 51.0% by weight, the weight average molecular weight (Mw) was 202,000, the dispersity (Mw / Mn) was 2.9, and the double per mol of polymer molecule. The binding amount (mol number) was 7.1 mol.

[Synthesis Example 7]
In Synthesis Example 6, the charged composition was 440 g of 2-ethylhexyl acrylate, 400 g of n-butyl acrylate, 100 g of methyl methacrylate, 30 g of dimethylaminoethyl methacrylate, 30 g of methacrylic acid, 10 g of α-methylstyrene dimer (polymerization initiator) It was prepared in the same manner as in Synthesis Example 6 except that the reaction rate was changed to 13.0 mol times, and the reaction was stopped when the polymerization conversion rate was about 55% by weight. Next, 4.5 g of glycidyl methacrylate was reacted to obtain a polymer composition P-7.

  The obtained polymer composition P-7 was able to be produced without any problem in safety because no rapid heat generation was observed within the entire reaction time. In addition, the polymerization conversion rate of the polymer composition P-7 was 55.5% by weight, the weight average molecular weight (Mw) was 216,000, the dispersity (Mw / Mn) was 3.0, and the double per mol of polymer molecule. The binding amount (mol number) was 6.8 mol.

[Synthesis Example 8]
In Synthesis Example 1, except that α-methylstyrene dimer was changed to 0.4 g (2.6 mol times the polymerization initiator), it was prepared in the same manner as in Synthesis Example 1, and the polymerization conversion rate was about 20% by weight. The reaction was stopped at some point. Next, 5 g of glycidyl methacrylate was reacted to obtain a polymer composition P-8.

  The obtained polymer composition P-8 was not observed to be rapidly heated within the entire reaction time, and could be produced without any problem in safety. In addition, the polymerization conversion rate of the polymer composition P-8 was 22.4% by weight, the weight average molecular weight (Mw) was 210,000, the dispersity (Mw / Mn) was 2.4, and the double per mol of the polymer molecule. The binding amount (mol number) was 7.4 mol.

[Synthesis Example 9]
In Synthesis Example 1, a polymer composition P-9 was obtained in the same manner as in Synthesis Example 1 except that 3 g of glycidyl methacrylate was changed to 3 g of glycidyl acrylate.

  The obtained polymer composition P-9 was able to be produced without any problem in safety because no rapid heat generation was observed within the entire reaction time. Polymer composition P-9 had a polymerization conversion rate of 45.0% by weight, a weight average molecular weight (Mw) of 255,000, a dispersity (Mw / Mn) of 2.4, and double bonds per mol of polymer molecule. The amount (mol number) was 6.0 mol.

[Synthesis Example 10]
In Synthesis Example 1, heavy polymerization was conducted in the same manner as in Synthesis Example 1 except that the polymerization initiator was changed to 0.2 g of cumylperoxyneodecanoate (Nippon Park Mill ND, 10 hour half-life temperature 37 ° C.). A combined composition P-1A was obtained.

  The obtained polymer composition P-1A could be produced without any problem in safety because no rapid heat generation was observed within the entire reaction time. In addition, the polymerization conversion rate of the polymer composition P-1A was 44.5% by weight, the weight average molecular weight (Mw) was 251,000, the dispersity (Mw / Mn) was 2.7, and the double per mol of polymer molecule. The binding amount (mol number) was 8.8 mol.

[Synthesis Comparative Example 1]
In Synthesis Example 1, preparation of polymer composition P-1B was attempted in the same manner as in Synthesis Example 1 except that α-methylstyrene dimer was not used (0.0 mol times the polymerization initiator). . However, immediately after the polymerization initiator 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) was added, a rapid exotherm was observed and reaction runaway occurred. It was judged.

[Synthesis Comparative Example 2]
Preparation of polymer composition P-1C was attempted in the same manner as in Synthesis Example 1, except that α-methylstyrene dimer was changed to 0.1 g (0.7 mol times the polymerization initiator) in Synthesis Example 1. It was. However, since rapid heat generation was observed immediately after the polymerization initiator 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) was added, it was judged that the production conditions had a safety problem.

[Synthesis Comparative Example 3]
In Synthesis Example 1, the polymerization initiator is changed to 0.2 g of 2,2′-azobis (2-methylbutyronitrile) (V-59 (manufactured by Wako Pure Chemical Industries, Ltd., 10 hour half-life temperature 67 ° C.)). Except for the above, an attempt was made to prepare polymer composition P-1D in the same manner as in Synthesis Example 1. However, since a sudden exotherm was observed while raising the reaction temperature to 70 ° C., it was determined that the production conditions were problematic in terms of safety.

[Synthesis Comparative Example 4]
In Synthesis Example 1, preparation of polymer composition P-1E was attempted in the same manner as in Synthesis Example 1 except that the reaction temperature after adding the polymerization initiator was changed to 90 ° C. However, since rapid heat generation was observed immediately after the polymerization initiator 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) was added, it was judged that the production conditions had a safety problem.

[Synthesis Comparative Example 5]
In Synthesis Example 1, the preparation of polymer composition P-1F was attempted in the same manner as in Synthesis Example 1 except that the condition for raising the reaction temperature to 70 ° C. was changed to the condition for raising the temperature to 120 ° C. It was. However, since heating was continuously observed after the temperature was raised to 120 ° C., it was determined that the production conditions had a problem with safety.

[Synthesis Comparative Example 6]
In Synthesis Example 7, prepared in the same manner as in Synthesis Example 7 except that the charged composition was changed to 920 g of methyl methacrylate, 30 g of dimethylaminoethyl methacrylate, and 30 g of acrylic acid, and the polymerization conversion was about 50% by weight. The reaction was stopped at. Next, 2.5 g of glycidyl methacrylate was reacted to obtain a polymer composition P-10.

  The obtained polymer composition P-10 was able to be produced without any problem in safety because no rapid heat generation was observed within the entire reaction time. Polymer composition P-10 had a polymerization conversion of 50.2% by weight, a weight average molecular weight (Mw) of 203,000, a dispersity (Mw / Mn) of 2.0, and a double per mole of polymer molecule. The binding amount (mol number) was 3.6 mol.

[Synthesis Comparative Example 7]
In Synthesis Example 1, it was prepared in the same manner as in Synthesis Example 1 except that the charged composition was changed to 950 g of 2-ethylhexyl acrylate and 50 g of acrylic acid, and the reaction was stopped when the polymerization conversion was about 45% by weight. It was. Next, 2.5 g of glycidyl methacrylate was reacted to obtain a polymer composition P-11.

  The obtained polymer composition P-11 was not observed to have a rapid exotherm within the entire reaction time, and could be produced without any problem in safety. Polymer composition P-11 had a polymerization conversion rate of 45.0% by weight, a weight average molecular weight (Mw) of 250,000, a dispersity (Mw / Mn) of 2.3, and a double per mole of polymer molecule. The binding amount (mol number) was 4.4 mol.

[Synthesis Comparative Example 8]
In Synthesis Example 1, it was prepared in the same manner as in Synthesis Example 1 except that the charged composition was changed to 880 g of 2-ethylhexyl acrylate and 120 g of N-vinylpyrrolidone, and the reaction was performed when the polymerization conversion rate was about 45% by weight. Stopped. Next, 2.5 g of glycidyl methacrylate was reacted to obtain a polymer composition P-12.

  The obtained polymer composition P-12 was able to be produced without any problem in safety because no rapid heat generation was observed within the entire reaction time. In addition, the polymerization conversion rate of the polymer composition P-12 was 44.2% by weight, the weight average molecular weight (Mw) was 240,000, the dispersity (Mw / Mn) was 2.5, and the double per mol of polymer molecule. The binding amount (mol number) was 4.2 mol.

[Synthesis Comparative Example 9]
In Synthesis Example 1, a polymer composition P-13 was obtained in the same manner as in Synthesis Example 1 except that the reaction was stopped and glycidyl methacrylate was not reacted.

  The obtained polymer composition P-13 was not observed to have a rapid exotherm within the entire reaction time, and could be produced without any problem in safety. In addition, the polymerization conversion rate of the polymer composition P-13 was 45.5% by weight, the weight average molecular weight (Mw) was 256,000, the dispersity (Mw / Mn) was 2.6, and the double per mol of the polymer molecule. The binding amount (mol number) was 0.0 mol.

[Synthesis Comparative Example 10]
In Synthesis Example 1, after stopping the reaction, Polymer Composition P-14 was obtained in the same manner as in Synthesis Example 1 except that the amount of glycidyl methacrylate charged was 1.5 g.

  The obtained polymer composition P-14 was able to be produced without any problem in safety because no rapid heat generation was observed within the entire reaction time. In addition, the polymerization conversion rate of the polymer composition P-14 was 45.1% by weight, the weight average molecular weight (Mw) was 253,000, the dispersity (Mw / Mn) was 2.5, and the double per mol of polymer molecule. The binding amount (mol number) was 2.7 mol.

[Synthesis Comparative Example 11]
In the synthesis example 1, after stopping reaction, polymer composition P-15 was obtained like the synthesis example 1 except the glycidyl methacrylate preparation amount having been 10 g.

  The obtained polymer composition P-15 was not observed to have a rapid exotherm within the entire reaction time, and could be produced without any problem in safety. In addition, the polymerization conversion rate of the polymer composition P-15 was 45.4% by weight, the weight average molecular weight (Mw) was 253,000, the dispersity (Mw / Mn) was 2.9, and the double per mol of polymer molecule The binding amount (mol number) was 17.8 mol.

[Synthesis Comparative Example 12]
In Synthesis Example 1, except that α-methylstyrene dimer was changed to 25 g (4.1 mol times the polymerization initiator) and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) was changed to 8 g. Prepared in the same manner as in Synthesis Example 1, and the reaction was stopped when the polymerization conversion reached about 40% by weight. Next, 5 g of glycidyl methacrylate was reacted to obtain a polymer composition P-16.

  The obtained polymer composition P-16 was able to be produced without any problem in safety because no rapid heat generation was observed within the entire reaction time. In addition, the polymerization conversion rate of the polymer composition P-16 was 40.5% by weight, the weight average molecular weight (Mw) was 152,000, the dispersity (Mw / Mn) was 2.1, and the double per mol of polymer molecule The binding amount (mol number) was 5.3 mol.

[Synthesis Comparative Example 13]
In Synthesis Example 1, it was prepared in the same manner as in Synthesis Example 1 except that the reaction was stopped when the polymerization conversion rate was about 30% by weight. Next, 3.0 g of glycidyl methacrylate was reacted to obtain a polymer composition P-17.

  The obtained polymer composition P-17 was able to be produced without any problem in safety because no rapid heat generation was observed within the entire reaction time. In addition, the polymerization conversion rate of the polymer composition P-17 was 32.2% by weight, the weight average molecular weight (Mw) was 202,000, the dispersity (Mw / Mn) was 1.7, and the double per mol of the polymer molecule was The binding amount (mol number) was 4.3 mol.

[Synthesis Comparative Example 14]
In Synthesis Example 1, it was prepared in the same manner as in Synthesis Example 1 except that the reaction was stopped when the polymerization conversion rate was about 15% by weight. Next, 2.5 g of glycidyl methacrylate was reacted to obtain a polymer composition P-18.

  The obtained polymer composition P-18 was not observed to be rapidly heated within the entire reaction time, and could be produced without any problem in safety. In addition, the polymerization conversion rate of the polymer composition P-17 was 18.2% by weight, the weight average molecular weight (Mw) was 102,000, the dispersity (Mw / Mn) was 1.7, and the double per mol of the polymer molecule. The amount of bonding (mol number) was 1.8 mol.

[Synthesis Comparative Example 15]
In Synthesis Example 1, except that α-methylstyrene dimer was changed to 70 g (4.6 mol times the polymerization initiator) and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) was changed to 20 g. Prepared in the same manner as in Synthesis Example 1, and the reaction was stopped when the polymerization conversion reached about 95% by weight. Next, 3 g of glycidyl methacrylate was reacted to obtain a polymer composition P-19.

  The obtained polymer composition P-19 was able to be produced without any problem in safety because no rapid heat generation was observed within the entire reaction time. In addition, the polymerization conversion rate of the polymer composition P-19 was 92.0% by weight, the weight average molecular weight (Mw) was 18,000, the dispersity (Mw / Mn) was 1.7, and the double per mol of the polymer molecule was The amount of bonds (number of moles) was 0.4 mol.

[Synthesis Comparative Example 16]
In Synthesis Comparative Example 15, a polymer composition P-20 was obtained in the same manner as in Synthesis Comparative Example 15 except that the amount of glycidyl methacrylate charged was 200 g.

  The obtained polymer composition P-20 was not observed to be rapidly heated within the entire reaction time, and could be produced without any problem in safety. In addition, the polymerization conversion rate of the polymer composition P-20 was 91.0% by weight, the weight average molecular weight (Mw) was 17,000, the dispersity (Mw / Mn) was 1.8, and the double per mol of the polymer molecule. The binding amount (mol number) was 23.9 mol.

[Synthesis Comparative Example 17]
Using the same apparatus as in Synthesis Example 1, 830 g of 2-ethylhexyl methacrylate, 120 g of N-vinylpyrrolidone, 50 g of acrylic acid, 0.5 g of p-methoxyphenol, 3 g of glycidyl methacrylate, N, N′-dimethylbenzylamine 4 g was charged and reacted at 90 ° C. for 6 hours while bubbling air into the flask to obtain a composition P-21 containing no polymer.

  The composition P-21 not containing a polymer was not observed to have a rapid exotherm within the entire reaction time, and could be produced without any problem in safety.

  The composition ratios and reaction conditions of the above synthesis examples and synthesis comparative examples are shown in Tables 1 to 3, respectively. Under conditions such as Synthesis Comparative Examples 1 to 5, heat generation control of solventless polymerization is insufficient, but heat generation is controlled in Synthesis Examples 1 to 10 prepared under the production conditions of the present invention. It can be seen that a photocurable useless composition that exhibits excellent adhesive properties can be easily prepared without problems in safety as shown in FIG.

The abbreviations in Tables 1 to 3 represent the following compounds.
Β-CEA: A mixture of acrylic acid and 2-carboxyethyl acrylate oligomer (n = 1-6), Rhodia Nikka Co., Ltd. V-70: 2,2′-azobis (4-methoxy-2,4-dimethyl Valeronitrile), 10-hour half-life temperature 30 ° C., manufactured by Wako Pure Chemical Industries, Ltd. Parkmill ND: Cumylperoxyneodecanoate, 10-hour half-life temperature 37 ° C., NOF Corporation V-59: 2,2 ′ -Azobis (2-methylbutyronitrile), 10 hour half-life temperature 67 ° C, manufactured by Wako Pure Chemical Industries, Ltd.

[Examples 1-11, Comparative Examples 1-14]
The solvent-free polymerizable polymer compositions P-1 to P-21 obtained in Synthesis Examples 1 to 9 and Synthesis Comparative Examples 6 to 17 were used, and the polymer compositions were used in the weight ratios shown in Tables 4 to 6. The product, chlorinated polypropylene, and photopolymerization initiator were charged into a 2 L four-necked flask having an air introduction tube, a reflux condenser, a stirring device, and a charging port, and stirred while bubbling air to keep the temperature at 50 ° C. It melted and mixed for 1 hour as it was, and obtained 35 types of photocurable solventless compositions (Examples 1-11, Comparative Examples 1-14).

  Tables 4 to 6 show the curing characteristics and adhesion characteristics of the obtained photocurable solventless composition.

  In Tables 4 to 6, the materials used are as follows.

Solvent-free polymerizable polymer composition (A)
Polymer compositions P-1 to P-21: those obtained in Synthesis Examples 1 to 9 and Synthesis Comparative Examples 6 to 17 described above Chlorinated polypropylene (B)
DX-530P: Toyobo Co., Ltd. chlorinated polypropylene DX-523P: Toyobo Co., Ltd. Chlorinated polypropylene Photopolymerization initiator (C)
・ Lucirin TPO: 2,4,6-trimethylbenzoyldiphenylphosphine = oxide, manufactured by BASF Japan ・ IRGACURE 184: 1-hydroxycyclohexyl phenyl ketone, manufactured by chiba

  In the evaluation results of the photocurable solventless compositions of the examples and comparative examples, the low molecular weight resin composition equivalent to the conventional low molecular weight resin composition having the reactive double bond as in Comparative Examples 10 and 11 is insufficient in curability. Thus, it can be seen that when the adhesive performance is lowered, or the amount of reactive double bonds is increased to maintain the curability, the film is too hard and the transfer performance is not exhibited. Further, it can be seen that the photocured monomer and the oligomer as in Comparative Example 11 as in Comparative Example 12 do not cure due to insufficient accumulated light amount when irradiated with low-intensity light (UV).

  On the other hand, the photocurable compositions of the present invention shown in Examples 1 to 11 have sufficient curability with very low strength and low integrated light quantity, and the adhesive performance including transfer performance is well expressed. I understand that.

  Moreover, it turned out that the composition and quantity which were set by this invention were required for expression of favorable adhesive performance from the comparison of Comparative Examples 1-6 and 13, 14 and an Example, and it used especially by Comparative Examples 4-6. From comparison with the polymer compositions P-13 to 15, it can be seen that good transfer performance is expressed only when the number of moles of double bonds per mole of polymer molecules is in an appropriate range.

Claims (8)

A photocurable solventless composition comprising a solvent, a solventless polymerizable copolymer composition (A) not containing a plasticizer, a chlorinated polypropylene (B), and a polymerization initiator (C) that absorbs ultraviolet rays to generate radicals The solvent-free polymerizable copolymer composition (A) is a (meth) acrylic acid ester monomer (a) having an alkyl group having 4 or more carbon atoms, and a polymerization having a nitrogen atom in the molecule. Monomer (b), a (meth) acrylic acid ester copolymer consisting of a (meth) acrylic acid ester monomer (c) represented by the following general formula (1), and the monomer (a) ( b) A mixture of (c), wherein the (meth) acrylic acid ester copolymer has a weight average molecular weight (Mw) of 200 to 400,000, and a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) ( Mw / Mn) has a dispersity represented by 2.0 to 5.0, and In addition to having 3 to 10 mol of polymerizable double bonds per mol of copolymer molecules in the side chain, the amount of the chlorinated polypropylene (B) is 1 to 8% by weight, and the amount of the polymerization initiator (C) is 0. A photocurable solventless composition characterized by being 5 to 8 % by weight .

(In the formula, R ¹ represents a hydrogen atom or a methyl group, n represents an integer of 0 to 6, and a plurality of n may be mixed.)   The photocurable solventless composition according to claim 1, wherein the polymerizable monomer (b) having a nitrogen atom in the molecule is N-vinylpyrrolidone and / or dimethylaminoethyl methacrylate.   The (meth) acrylic acid ester copolymer is obtained by copolymerizing 20 to 60% by weight of the total amount of the monomer mixture composed of the monomers (a), (b) and (c). The photocurable solventless composition according to claim 1, wherein the composition is a photocurable solventless composition.   The photocurable solventless composition according to claim 1, wherein the (meth) acrylic acid ester copolymer is copolymerized by living radical polymerization. It is a manufacturing method of the photocurable solventless composition in any one of Claims 1-4 , Comprising: The (meth) acrylic acid ester monomer (a) which has an alkyl group with 4 or more carbon atoms, intramolecular A monomer mixture comprising a polymerizable monomer (b) having a nitrogen atom and a (meth) acrylate monomer (c) represented by the following general formula (1): A solvent-free polymerizable copolymer composition containing no solvent or plasticizer by copolymerizing a (meth) acrylic acid ester copolymer so that the conversion rate is 20 to 60% by weight in the total amount of the mixture. A method for producing a photocurable solventless composition, comprising preparing (A) and dissolving and mixing chlorinated polypropylene (B) and a polymerization initiator (C) that absorbs ultraviolet rays to generate radicals.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, n represents an integer of 0 to 6, and a plurality of n may be mixed.) The said (meth) acrylic acid ester copolymer is copolymerized by living radical polymerization, The manufacturing method of the photocurable solventless composition of Claim 5 characterized by the above-mentioned. The living radical polymerization is addition-cleavage-type chain transfer polymerization, and the addition-open-chain-type chain transfer agent (d) is used at least 2 mol times the polymerization initiator (e) whose 10-hour half-life temperature is 30 to 50 ° C. The method for producing a photocurable solventless composition according to claim 6 , wherein after the first polymerization reaction is performed at 50 ° C. or less, the second polymerization reaction is performed at 60 to 100 ° C. 8. After copolymerizing the (meth) acrylic acid ester copolymer, a polymerizable double bond is introduced into the side chain of the copolymer by reacting with glycidyl acrylate or glycidyl methacrylate. method for producing a photocurable type non solvent composition according to any one of claims 5-7.