JP5561986B2 - Photocurable resin composition and adhesive polymer gel - Google Patents

Description

  The present invention relates to a photocurable resin composition and an adhesive polymer gel. More specifically, the present invention relates to a photocurable resin composition used when producing an adhesive tape, a polymer gel, and the like, and an adhesive polymer gel obtained using the same.

Adhesive polymer gels are widely used as biomaterials, medical materials, sanitary materials, and industrial materials. Various types of gel are known as adhesive polymer gels.
As a method for producing an adhesive polymer gel, there is a method obtained by heating and crosslinking a mixed liquid of a polymer such as polyacrylic acid and a polyfunctional epoxy compound.
However, in the mixture that undergoes a thermosetting reaction, the reaction proceeds even at room temperature immediately after mixing the polymer containing a carboxyl group and the crosslinking agent. Therefore, if it is not used up within a certain period of time, it will gel and waste raw materials. In other words, since pot life exists, it is necessary to mix in small increments and supply it to the coating line.

Even if a cross-linking agent is added to the resin, it is fluid within the pot life and can be supplied to the coating line, but strictly speaking, the reaction proceeds gradually, and the quality of the product It can be a factor of variation.
Furthermore, since it gels in a short time, it is difficult to sufficiently defoam bubbles generated by stirring for mixing with a crosslinking agent, etc. Especially when the stock solution has a high viscosity, bubbles are mixed into the product. Problem arises.
An adhesive polymer gel using ion crosslinking using a polyvalent metal ion such as aluminum also exists as a method of causing a moderately moderate crosslinking reaction. However, also in this gel, a crosslinking reaction starts simultaneously with mixing a carboxyl group-containing polymer and a crosslinking agent containing a polyvalent metal, or adding a catalyst such as an acid. Therefore, as described above, it is difficult to completely stop the reaction.

Therefore, there is a method of forming a gel using a photocuring reaction. According to this method, if the light is blocked and stored, gelation does not occur, the stability is longer than that using a thermosetting reaction, and the problem of air bubbles in the gel product can also be reduced. (Unexamined-Japanese-Patent No. 2005-213349: patent document 1).
In the above publication, a cross-linking in which an epoxy compound is subjected to an epoxy ring-opening addition reaction on at least a part of a carboxy group and a phenolic hydroxyl group of a resin having a carboxyl group in a side chain and at least one of a carboxyl group and a phenolic hydroxyl group in a side chain. A photosensitive resin composition containing a photosensitive resin (A), a photopolymerization initiator (B), and water (C), and a hydrogel obtained by curing the photosensitive resin composition are described. Yes.

JP 2005-213349 A

  However, the water-containing gel obtained from the photosensitive resin composition described in the above publication is excellent in gel strength but not sufficient in adhesiveness. This invention provides the photocurable resin composition from which the gel excellent in adhesiveness is easily obtained by light irradiation, and the adhesive polymer gel obtained from it.

Thus, according to the present invention, a photocurable prepolymer obtained by adding a monomer having a glycidyl group and a vinyl group to a polymer containing a carboxy group, a photopolymerization initiator, and a polyhydric alcohol 3 A photocurable resin composition containing components and containing 30 to 80% by weight of the polyhydric alcohol with respect to the three components is provided.
Furthermore, according to the present invention, there is provided an adhesive polymer gel obtained by curing the photocurable resin composition.

Since the photocurable resin composition of the present invention undergoes a crosslinking reaction by light, it can be stored for a long period of time without being gelled if stored in the dark and can be stored for a long period of time. A gel can be obtained easily. Moreover, since it is not necessary to mix a crosslinking agent just before coating, it can be coated in a sufficiently defoamed state, and a good product can be obtained.
Moreover, when the polyhydric alcohol is contained in an amount of 50 to 80% by weight with respect to the three components, an adhesive polymer gel having more excellent adhesiveness can be easily obtained.

Furthermore, when the polyhydric alcohol is selected from (poly) ethylene glycol, (poly) propylene glycol, (poly) butanediol, (poly) pentanediol, glycerin and polyglycerin, a tacky polymer having excellent tackiness A gel can be obtained easily.
Moreover, when the polymer containing a carboxy group and the monomer having the glycidyl group and the vinyl group are contained in an amount of 20 to 70% by weight and 0.1 to 2.0% by weight with respect to the three components, the adhesiveness is excellent. An adhesive polymer gel can be easily obtained.

Furthermore, when the polymer containing a carboxy group has a weight average molecular weight of 30,000 to 350,000, an adhesive polymer gel excellent in adhesiveness can be easily obtained.
Also, polymers containing carboxyl groups, having a (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, derived from a monomer that will be selected from crotonic acid, and allyl carboxylic acid, the weight average molecular weight of from 30000 to 350000 In this case, an adhesive polymer gel excellent in adhesiveness can be easily obtained.

Furthermore, when the monomer having a glycidyl group and a vinyl group is selected from glycidyl (meth) acrylate, allyl glycidyl ether and hydroxybutyl acrylate glycidyl ether, it is possible to easily obtain an adhesive polymer gel excellent in adhesiveness. it can.
The photocurable resin composition further includes water and an inorganic salt that dissolves in water, and the water and the inorganic salt are 0.1 to 10 parts by weight and 0.003 to 0.003 by weight with respect to 1 part by weight of the polyhydric alcohol. When 0.1 weight part is contained, the adhesive polymer gel which has the electroconductivity excellent in adhesiveness can be provided. The adhesive polymer gel having conductivity is particularly useful in the field where it is required to have both adhesion and conductivity, such as an electrocardiographic electrode.

The adhesive polymer gel of the present invention comprises a cured product obtained by curing a photocurable resin composition containing the following three components. The three components are a photocurable prepolymer, a photopolymerization initiator, and a polyhydric alcohol.
(Photo-curable prepolymer)
A photocurable prepolymer is obtained by adding a monomer having a glycidyl group and a vinyl group to a polymer containing a carboxy group.
(1) As a polymer containing a carboxy group, for example, a homopolymer derived from a carboxy group-containing monomer such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and allylcarboxylic acid, Mention may be made of copolymers. The number of carboxy groups present in the polymer is preferably 600 or more, for example. In addition, (meth) acryl means acryl or methacryl.

Furthermore, the polymer containing a carboxy group may be a copolymer of the above monomer and another monomer that can be copolymerized with the above monomer. Examples of such other monomers include (meth) acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, acrylamide-2-methylpropanesulfonic acid, acrylamide derivatives such as acryloylmorpholine, Examples thereof include acrylic acid derivatives such as alkyl (meth) acrylate (wherein alkyl has 1 to 4 carbon atoms, for example), and polar monomers such as vinyl pyrrolidone.
The polymer containing a carboxy group preferably contains a unit derived from the carboxy group-containing monomer in a proportion of 50% by weight or more. More preferably, the polymer containing a carboxy group is derived only from a carboxy group-containing monomer. In particular, a polymer derived only from (meth) acrylic acid is preferable.

  Although the polymer containing a carboxy group varies depending on the type of monomer constituting it, it preferably has a molecular weight of 30,000 to 350,000. When the molecular weight is less than 30,000, the shape retention of the adhesive polymer gel may be lowered. When molecular weight is larger than 350,000, the softness | flexibility and adhesiveness of adhesive polymer gel may fall. A more preferable molecular weight is 40,000 to 300,000. Here, the molecular weight is a value measured by gel permeation chromatography.

The polymer containing a carboxy group may be a polymer having the same molecular weight consisting of only the same monomer, or may be a mixture of polymers having the same monomer but different molecular weights. It may be a mixture. Among these, it is preferable that the polymer containing a carboxy group is composed of only the same monomer but is a mixture of polymers having different molecular weights, since it is possible to further suppress the deterioration of the adhesive with time. For example, in the case of a mixture of two different molecular weight polymers, the difference in molecular weight is preferably about 50,000 to 300,000.
The polymer containing a carboxy group is contained in an amount of 20 to 70% by weight based on the above three components. When the content is less than 20% by weight, the shape retention of the adhesive polymer gel may be lowered. When there is more content than 70 weight%, the softness | flexibility of adhesive polymer gel falls and adhesiveness may fall.

(2) Examples of the monomer having a glycidyl group and a vinyl group include glycidyl (meth) acrylate, allyl glycidyl ether, and hydroxybutyl acrylate glycidyl ether. These monomers may be used alone or in combination.
A monomer having a glycidyl group and a vinyl group is contained in an amount of 0.1 to 2.0% by weight based on the three components. When the content is less than 0.1% by weight, the shape retention of the adhesive polymer gel may be lowered. When the content is more than 2.0% by weight, the adhesive polymer gel may become brittle. A more preferable content is 0.1 to 1.0% by weight.

  Furthermore, it is preferable that the monomer which has a glycidyl group and a vinyl group is contained in the ratio of 0.003-0.1 weight part with respect to 1 weight part of polymers containing a carboxy group. When this ratio is less than 0.003 part by weight, the shape retention of the adhesive polymer gel may be lowered. When the ratio is more than 0.1 parts by weight, the adhesive polymer gel may become brittle. A more desirable ratio is 0.005 to 0.05 part by weight.

(3) Production Method of Photocurable Prepolymer The addition of a monomer having a glycidyl group and a vinyl group to a polymer containing a carboxy group is not particularly limited and can be performed by a known method. For example, a polymer solution is obtained by dissolving a polymer containing a carboxy group in a solvent (for example, water). This polymer solution may contain a known plasticizer (for example, a polyhydric alcohol described below). The dissolution may be performed while heating. Since the viscosity of the polymer can be lowered by heating, the dissolution time can be shortened. Next, the temperature of the polymer solution is adjusted to a range of 50 to 60 ° C., and after temperature stabilization, a monomer having a glycidyl group and a vinyl group is added to the polymer solution. After the addition, for example, by maintaining stirring of the polymer solution for about 1.5 hours, a photocurable prepolymer obtained by adding a monomer having a glycidyl group and a vinyl group to a polymer containing a carboxy group can be obtained.
The photocurable prepolymer obtained by the above method may be isolated from the solvent, or may be used as it is for the production of the photocurable resin composition without isolation.

(Photopolymerization initiator)
The photopolymerization initiator is not particularly limited as long as it can generate radicals by cleavage with ultraviolet rays or visible rays. For example, α-hydroxyketone, α-aminoketone, benzylmethyl ketal, bisacylphosphine oxide, metallocene and the like can be mentioned. In addition to these photopolymerization initiators, commercially available 2-hydroxy-2-methyl-1-phenyl-propan-1-one (product name: Darocur 1173, manufactured by Ciba Specialty Chemicals), 1- Hydroxy-cyclohexyl-phenyl-ketone (product name: Irgacure 184, manufactured by Ciba Specialty Chemicals), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methylpropan-1-one ( Product name: Irgacure 2959, manufactured by Ciba Specialty Chemicals), 2-methyl-1-[(methylthio) phenyl] -2-morpholinopropan-1-one (Product name: Irgacure 907, manufactured by Ciba Specialty Chemicals) 2-benzyl-2-dimethylamino-1- (4-morpholinopheny ) - butane-1-one (product name: Irgacure 369, manufactured by Ciba Specialty Chemicals, Inc.), and the like can also be used. These photopolymerization initiators may be used alone or in combination.

The addition amount of a photoinitiator can be suitably set according to hardening conditions, such as the irradiation intensity of light to the photocurable resin composition, and the irradiation time of light. For example, it can set to the range of 0.005-5 weight part with respect to 100 weight part of photocurable prepolymers.
When it is desired to complete the curing in a short time or when it is desired to reduce the light irradiation intensity, it is necessary to set a large amount of the photopolymerization initiator. On the other hand, when the curing can be performed for a long time, or when the irradiation intensity of light can be increased, the addition amount of the photopolymerization initiator can be set small.
For example, the intensity of light irradiation can be set to 40 to 400 mW / cm ² , the irradiation time can be set to 10 to 30 seconds, and the irradiation energy can be set to 500 to 5000 mJ / cm ² .

(Polyhydric alcohol)
The polyhydric alcohol imparts adhesiveness to the adhesive polymer gel and plasticity. Examples of the polyhydric alcohol include diols such as (poly) ethylene glycol, (poly) propylene glycol, (poly) butanediol, and (poly) pentanediol, polyol, glycerin, polyglycerin and the like. In the above examples, the number of repeating units in the diol and the number of repeating units in the polyglycerol are preferably 2-6. These polyhydric alcohols may be used alone or in combination.
The polyhydric alcohol is contained in an amount of 30 to 80% by weight with respect to the three components. When the content of the polyhydric alcohol is less than 30% by weight, sufficient tackiness may not be obtained. When it is more than 80% by weight, the shape-retaining property of the adhesive polymer gel may be lowered, or the conductivity may be lowered. A preferable content is 50 to 80% by weight.

(Other ingredients)
(1) Water and inorganic salt The adhesive polymer gel may further contain water and an inorganic salt dissolved in water in order to impart conductivity.
The water may contain an organic solvent such as a lower alcohol, if necessary. Examples of inorganic salts include sodium chloride, potassium chloride, magnesium chloride and the like.

It is preferable that 0.1-10 weight part and 0.003-0.1 weight part of water and inorganic salt are contained with respect to 1 weight part of polyhydric alcohol. When the addition amount of water is less than 0.1 part by weight and the addition amount of the inorganic salt is less than 0.003 part by weight, the conductivity of the adhesive polymer gel may not be sufficiently obtained. When the amount of water added is more than 10 parts by weight, the adhesive strength of the adhesive polymer gel may be reduced.
The water and inorganic salt are more preferably contained in 0.2 to 3 parts by weight and 0.006 to 0.05 parts by weight with respect to 1 part by weight of the polyhydric alcohol.
(2) The adhesive polymer gel may contain other known additives such as pigments, dyes, preservatives, antioxidants, ultraviolet absorbers, and tackifiers.

(Adhesive polymer gel)
The adhesive polymer gel is obtained by curing the photocurable resin composition.
(1) Manufacturing method of photocurable resin composition A photocurable resin composition is obtained by mixing three components of a photocurable prepolymer, a photopolymerization initiator, and a polyhydric alcohol, and optionally other components. Can be obtained. Here, the photocurable prepolymer can be obtained by adding a monomer having a glycidyl group and a vinyl group, but the photopolymerization initiator, polyhydric alcohol and other components are allowed to coexist in the reaction system at the time of addition. It may be mixed with the photocurable prepolymer after addition. Moreover, a photoinitiator, a polyhydric alcohol, and other components may be added simultaneously or at different times. In particular, if the photopolymerization initiator is present in the photocurable resin composition at an early stage, the photocurable prepolymer may be gradually cured, so it is preferable to be present at the latest stage. Below, an example of the manufacturing method of a photocurable resin composition is shown.

  First, a polymer containing a carboxy group is dissolved in a polyhydric alcohol. The melting temperature is not particularly limited. Moreover, when there is an oil-soluble component in other components, it may be dissolved in a polyhydric alcohol in advance. Furthermore, you may add the liquid mixture of water and the inorganic salt for providing electroconductivity to adhesive polymer gel to this solution. The obtained solution may have a liquid property such as pH as necessary.

Next, after adding the monomer which has a glycidyl group and a vinyl group to the said solution, the monomer which has a glycidyl group and a vinyl group is added to the polymer containing a carboxy group. For the addition, the conditions described in the column of the photocurable prepolymer can be adopted.
A photocurable resin composition can be obtained by adding a photopolymerization initiator to the mixed liquid obtained by the above addition. The addition of the photopolymerizable initiator is preferably after the temperature of the mixed solution has been lowered to, for example, 30 ° C. or lower in order to suppress the decomposition.

(2) Manufacturing method of adhesive polymer gel As the curing conditions of the photocurable resin composition for obtaining the adhesive polymer gel, the conditions described in the column of the photocurable prepolymer can be adopted.
(3) Properties of adhesive polymer gel The adhesive polymer gel of the present invention not only has an improved initial adhesive force, but also suppresses a decrease in adhesive force after aging. For example, both the initial adhesive strength and the adhesive strength after aging can be 0.25 N or more. In particular, both adhesive forces can be 0.5 N or more. The adhesive polymer gel having both adhesive forces of 0.5 N or more is, for example, 50 to 80% by weight of the polyhydric alcohol with respect to the three components, and 0.2% of the water to 1 part by weight of the polyhydric alcohol. It can obtain by making it-3 weight part.

  Furthermore, when the adhesive polymer gel contains water and an inorganic salt, conductivity can be imparted to the adhesive polymer gel. For example, conductivity of 150Ω or less can be imparted by evaluating with impedance. In particular, conductivity of 100Ω or less can be imparted. The conductive polymer gel having a conductivity of 100Ω or less is, for example, 50 to 80% by weight of polyhydric alcohol with respect to three components, and 0.2 to 0.2 parts by weight of water and inorganic salt with respect to 1 part by weight of polyhydric alcohol. It can obtain by setting it as 3 weight part and 0.003-0.05 weight part.

(4) Shape of Adhesive Polymer Gel The adhesive polymer gel is usually formed into a polymer by gelling a liquid photocurable resin composition, so that it can be appropriately molded according to the intended use. For example, when using as an adhesive tape, it is desirable to shape | mold into the sheet form whose thickness is 0.01-2.0 mm.
In the case of a sheet, it is preferable to provide separators for protecting the surface on both sides of the adhesive polymer gel. One of the separators may be a support. The other is preferably attached to the final product as a base film. In this case, the separator can be peeled off immediately before use by the end user. In addition, a support body points out things, such as a film for reinforcing the adhesive polymer gel and maintaining the form of a tape, a nonwoven fabric, a woven fabric. Usually, the adhesive polymer gel is coated on a support and used as a so-called adhesive tape.

  The material of the separator is not particularly limited as long as it is a resin or paper that can be molded into a film. Among these, a resin film made of polyester, polyolefin, polystyrene, polyurethane, polyamide, polyimide, paper, paper laminated with a resin film, or the like is preferably used. In particular, when used as a base film, a biaxially stretched PET film, or a paper laminated with OPP or polyolefin is preferable. Furthermore, you may improve the adhesiveness of adhesive polymer gel and a base film by laminating a nonwoven fabric on a base film.

  The surface of the separator that contacts the adhesive polymer gel is preferably subjected to a mold release treatment. Further, both sides of the separator may be subjected to release treatment as necessary. When performing release treatment on both sides, a difference may be made in the peel strength between the front and back sides. Examples of the mold release treatment method include a silicone coating, and in particular, a baking type silicone coating which is crosslinked or cured by heat or ultraviolet rays is preferable.

  Among the separators, an optimal material for the top film disposed on the opposite surface of the base film is selected according to the product form of the adhesive polymer gel. For example, when the adhesive polymer gel is handled as a strip, it is not particularly limited as long as it is a resin or paper that can be formed into a film as described above, but it is preferable that the release treatment is performed in the same manner as the base film.

  Moreover, as a support body, the resin film which has or has not been mold-released can be used. Examples of the resin film include polyester, polyolefin, polystyrene, polyurethane, polyamide, and polyimide. For example, in the case of an adhesive polymer gel for biological use, it is desired to use a support having flexibility and water vapor permeability. In this case, polyurethane and polyol-modified polyester are known which have flexibility and water vapor permeability. Of these, polyol-modified polyester is preferred. When the support having flexibility is used alone, it may be difficult to handle the adhesive polymer gel during production. In that case, polyolefin, polyester, paper or the like may be laminated on a flexible support.

  The adhesive polymer gel provided with the above support is, for example, a method of sticking the support after the formation of the adhesive polymer gel, and a photo-curable resin composition is directly coated on the support and then irradiated with ultraviolet rays. Can be produced by a method for producing a conductive polymer gel. Moreover, the double-sided adhesive tape from which adhesive force differs by front and back can be obtained by sticking the adhesive polymer gel from which adhesive force differs to each of the front and back surfaces of a support body.

  In the adhesive polymer gel, a nonwoven fabric or a woven fabric may be embedded as an intermediate base material as necessary. When the adhesive polymer gel is formed into a sheet shape, these intermediate base materials play a role of reinforcing the adhesive polymer gel and improving the shape retention during cutting. As the material of the nonwoven fabric and the woven fabric, natural fibers such as cellulose, silk and hemp, synthetic fibers such as polyester, nylon, rayon, polyethylene, polypropylene and polyurethane, or a blend thereof can be used. The nonwoven fabric and the woven fabric may be bound by a binder, may be colored, or may be subjected to a conductive treatment, as necessary.

  Moreover, you may use a film instead of a nonwoven fabric and a woven fabric. Usable films include resin films such as polyester, polyolefin, polystyrene, and polyurethane. These films may have holes, have a multilayer structure, or may be colored.

(5) Use of adhesive gel The gel and adhesive tape of the present invention can be widely used as biomaterials, medical materials, hygiene materials, industrial materials, and the like. As biomaterials, medical materials and hygiene materials, surgical tapes, fixing tapes for sensors such as catheters, infusion tubes, electrocardiogram electrodes, poultices, wound dressings, colostomy tapes, Examples thereof include a conductor for an electrotherapy device, an adhesive for fixing a magnetic therapy device, and a carrier / adhesive for a transdermal absorbent. Industrial materials such as adhesives and conductive materials in the field of building materials and electronic materials, display (PDP, liquid crystal display, etc.) and touch panel spacers, fillers, vibration-proof materials, shock absorbers and shock absorbers, and gels for batteries And the like.

Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to this. In addition, the evaluation method of each property in an Example and a comparative example is described below.
(Adhesive force)
The adhesive strength is measured immediately after production and after drying. Specifically, the adhesive strength of the adhesive polymer gel immediately after production is measured. Next, the adhesive polymer gel is dried by allowing it to stand for 20 hours at room temperature (22-23 ° C.) and a humidity of 57-63%. The adhesive strength of the adhesive polymer gel after drying is measured.
The adhesive strength is measured by a vertical tensile test method. Specifically, a weight having a diameter of 12 mm and a mass of 10 g is placed on the adhesive surface of the adhesive polymer gel. Ten seconds after mounting, the weight is pulled up at a speed of 50 mm / min. The maximum load when the weight is peeled off from the adhesive polymer gel is defined as the adhesive force.

(Impedance)
Impedance is measured immediately after manufacture and after drying. Specifically, the impedance of the adhesive polymer gel immediately after production is measured. Next, the adhesive polymer gel is dried by allowing it to stand at room temperature (22 to 23 ° C.) and a humidity of 57 to 63% for 20 hours. The impedance of the adhesive polymer gel after drying is measured.
The impedance of the adhesive polymer gel is such that a 10 mm × 10 mm square adhesive polymer gel is sandwiched between two electrode plates (copper nickel plated plate, thickness 0.5 to 10 mm, length 10 mm × width 10 mm). . A load in the thickness direction of 500 g is applied to the sandwiched adhesive polymer gel, and the impedance is measured using an LCR meter (sine wave, 1 Vp-p, 1 kHz).

Example 1
(1) Production Method of Photocurable Resin Composition 0.051 g of methyl parahydroxybenzoate as a preservative is dissolved in 11.53 g of glycerin (product name: Pharmacopoeia Glycerin, manufactured by Nippon Oil & Fats Co., Ltd.), a polyhydric alcohol. It was. Thereafter, an aqueous solution of polyacrylic acid having a molecular weight of about 200 to 300,000, which is a polymer containing a carboxy group (product name: Jurimer AC-10H, polyacrylic acid content 19 to 21% by weight, Nippon Pure Chemical) (Manufactured by Co., Ltd.) 4.52 g of polyacrylic acid powder (product name: Jurimer AC-10LP, manufactured by Nippon Pure Chemical Co., Ltd.) 4.59 g, antioxidant, sodium bisulfite 0.029 g, solvent 7.97 g of ion-exchanged water was dissolved. The resulting solution was heated to 50 ° C., and 1.84 g of sodium hydroxide was added in portions to neutralize the solution. In the neutralized solution, 0.117 g of sodium chloride as an electrolyte was dissolved.

The above solution is heated to 60 ° C., and 0.06 g of glycidyl dimethacrylate (product name: Blemmer G, manufactured by NOF Corporation), which is a monomer having a glycidyl group and a vinyl group, is added, followed by stirring for 1.5 hours Thus, glycidyl methacrylate was added to the carboxy group in the polyacrylic acid.
After cooling the solution after addition to 30 ° C., 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methylpropan-1-one (product name: Irgacure) which is a photopolymerization initiator 2959 was added to the Ciba Specialty Chemicals Inc.) 3.0 × 10 ^-4 g solution. After the addition, the photopolymerization initiator was dissolved by stirring to obtain a colorless and transparent photocurable resin composition.

(2) Manufacturing method of adhesive polymer gel The said photocurable resin composition was dripped on PET film by which silicone coating was carried out. A silicone-coated PET film coated with silicone was placed on the drop to spread the drop to a uniform thickness (1.0 mm) between the films, and then both films were fixed at that thickness. .
Next, an adhesive polymer gel having a thickness of 1.0 mm was obtained by irradiating the photocurable resin composition with ultraviolet rays having an energy amount of 3000 mJ / cm ² using a metal halide lamp. The obtained adhesive polymer gel was colorless and transparent, and no bleeding phenomenon of polyhydric alcohol or water was observed.

  The tackiness and impedance of the obtained tacky polymer gel were measured, and the results are shown in Table 1. The adhesive polymer gel was stored at room temperature (22-23 ° C.) and humidity of 57-63% for 20 hours, and then the weight change rate, adhesiveness and impedance of the adhesive polymer gel were measured. The results are shown in Table 1.

Example 2
An adhesive polymer gel was obtained in the same manner as in Example 1 except that the addition amount of glycidyl dimethacrylate was changed from 0.06 g to 0.03 g. The obtained adhesive polymer gel was colorless and transparent, and no bleeding phenomenon of polyhydric alcohol or water was observed. The tackiness and impedance of the obtained tacky polymer gel were measured, and the results are shown in Table 1. The adhesive polymer gel was stored at room temperature (22-23 ° C.) and humidity of 57-63% for 20 hours, and then the weight change rate, adhesiveness and impedance of the adhesive polymer gel were measured. The results are shown in Table 1.

Example 3
An adhesive polymer gel was obtained in the same manner as in Example 1 except that the addition amount of glycidyl dimethacrylate was changed from 0.06 g to 0.09 g. The obtained adhesive polymer gel was colorless and transparent, and no bleeding phenomenon of polyhydric alcohol or water was observed. The tackiness and impedance of the obtained tacky polymer gel were measured, and the results are shown in Table 1. The adhesive polymer gel was stored at room temperature (22-23 ° C.) and humidity of 57-63% for 20 hours, and then the weight change rate, adhesiveness and impedance of the adhesive polymer gel were measured. The results are shown in Table 1.

Example 4
The adhesiveness was changed in the same manner as in Example 1 except that the addition amount of glycerin was changed from 11.53 g to 3.56 g, the addition amount of ion exchange water was changed from 7.97 g to 15.94 g, and ultraviolet light was changed to visible light. A polymer gel was obtained. The obtained adhesive polymer gel was colorless and transparent, and no bleeding phenomenon of polyhydric alcohol or water was observed. The tackiness and impedance of the obtained tacky polymer gel were measured, and the results are shown in Table 1. The adhesive polymer gel was stored at room temperature (22-23 ° C.) and humidity of 57-63% for 20 hours, and then the weight change rate, adhesiveness and impedance of the adhesive polymer gel were measured. The results are shown in Table 1.

Example 5
The adhesiveness was changed in the same manner as in Example 1 except that the addition amount of glycerin was changed from 11.53 g to 4.75 g, the addition amount of ion exchange water was changed from 7.97 g to 14.75 g, and ultraviolet light was changed to visible light. A polymer gel was obtained. The obtained adhesive polymer gel was colorless and transparent, and no bleeding phenomenon of polyhydric alcohol or water was observed. The tackiness and impedance of the obtained tacky polymer gel were measured, and the results are shown in Table 1. The adhesive polymer gel was stored at room temperature (22-23 ° C.) and humidity of 57-63% for 20 hours, and then the weight change rate, adhesiveness and impedance of the adhesive polymer gel were measured. The results are shown in Table 1.

Example 6
An adhesive polymer gel was obtained in the same manner as in Example 1 except that the addition amount of glycerin was changed from 11.53 g to 7.84 g and the addition amount of ion-exchanged water was changed from 7.97 g to 11.66 g. The obtained adhesive polymer gel was colorless and transparent, and no bleeding phenomenon of polyhydric alcohol or water was observed. The tackiness and impedance of the obtained tacky polymer gel were measured, and the results are shown in Table 1. The adhesive polymer gel was stored at room temperature (22-23 ° C.) and humidity of 57-63% for 20 hours, and then the weight change rate, adhesiveness and impedance of the adhesive polymer gel were measured. The results are shown in Table 1.

Example 7
An adhesive polymer gel was obtained in the same manner as in Example 1 except that the addition amount of glycerin was changed from 11.53 g to 15.92 g and the addition amount of ion-exchanged water was changed from 7.97 g to 3.58 g. The obtained adhesive polymer gel was colorless and transparent, and no bleeding phenomenon of polyhydric alcohol or water was observed. The tackiness and impedance of the obtained tacky polymer gel were measured, and the results are shown in Table 1. The adhesive polymer gel was stored at room temperature (22-23 ° C.) and humidity of 57-63% for 20 hours, and then the weight change rate, adhesiveness and impedance of the adhesive polymer gel were measured. The results are shown in Table 1.

Example 8
The adhesive polymer gel was prepared in the same manner as in Example 1 except that the addition amount of glycerin was changed from 11.53 g to 19.48 g and the addition amount of ion-exchanged water was changed from 7.97 g to 0 g (no addition). Obtained. The obtained adhesive polymer gel was colorless and transparent, and no bleeding phenomenon of polyhydric alcohol or water was observed. The tackiness and impedance of the obtained tacky polymer gel were measured, and the results are shown in Table 1. The adhesive polymer gel was stored at room temperature (22-23 ° C.) and humidity of 57-63% for 20 hours, and then the weight change rate, adhesiveness and impedance of the adhesive polymer gel were measured. The results are shown in Table 1.

Comparative Example 1
An adhesive polymer gel was obtained in the same manner as in Example 1 except that the addition amount of glycerin was changed from 11.53 g to 0.24 g and the addition amount of ion-exchanged water was changed from 7.97 g to 19.26 g. The obtained adhesive polymer gel was cloudy, and no bleeding phenomenon of polyhydric alcohol or water was observed. The tackiness and impedance of the obtained tacky polymer gel were measured, and the results are shown in Table 1. The adhesive polymer gel was stored at room temperature (22-23 ° C.) and humidity of 57-63% for 20 hours, and then the weight change rate, adhesiveness and impedance of the adhesive polymer gel were measured. The results are shown in Table 1.

Comparative Example 2
An adhesive polymer gel was obtained in the same manner as in Example 1 except that the addition amount of glycerin was changed from 11.53 g to 1.19 g and the addition amount of ion-exchanged water was changed from 7.97 g to 18.31 g. The obtained adhesive polymer gel was cloudy, and no bleeding phenomenon of polyhydric alcohol or water was observed. The tackiness and impedance of the obtained tacky polymer gel were measured, and the results are shown in Table 1. The adhesive polymer gel was stored at room temperature (22-23 ° C.) and humidity of 57-63% for 20 hours, and then the weight change rate, adhesiveness and impedance of the adhesive polymer gel were measured. The results are shown in Table 1.

Comparative Example 3
An adhesive polymer gel was obtained in the same manner as in Example 1 except that the addition amount of glycerin was changed from 11.53 g to 2.38 g and the addition amount of ion-exchanged water was changed from 7.97 g to 17.13 g. The obtained adhesive polymer gel was cloudy, and no bleeding phenomenon of polyhydric alcohol or water was observed. The tackiness and impedance of the obtained tacky polymer gel were measured, and the results are shown in Table 1. The adhesive polymer gel was stored at room temperature (22-23 ° C.) and humidity of 57-63% for 20 hours, and then the weight change rate, adhesiveness and impedance of the adhesive polymer gel were measured. The results are shown in Table 1.

Table 1 shows the following.
It can be seen that the adhesive polymer gel of the example maintains the adhesive force and impedance (conductivity) even after aging.
On the other hand, since the polymer gel of the comparative example has a small amount of polyhydric alcohol, it can be seen that the adhesive strength immediately after production is insufficient and the impedance after aging cannot be maintained.
Examples 4 and 5 are adhesive polymer gels cured by visible light, but it can be seen that the adhesive strength and impedance are maintained even after aging.

Claims (9)

  It contains three components of a photocurable prepolymer obtained by adding a monomer having a glycidyl group and a vinyl group to a polymer containing a carboxy group, a photopolymerization initiator, and a polyhydric alcohol. A photocurable resin composition containing 30 to 80% by weight of alcohol based on three components.   The photocurable resin composition according to claim 1, wherein the polyhydric alcohol is contained in an amount of 50 to 80 wt% with respect to the three components.   The photocurable resin according to claim 1 or 2, wherein the polyhydric alcohol is selected from (poly) ethylene glycol, (poly) propylene glycol, (poly) butanediol, (poly) pentanediol, glycerin, and polyglycerin. Composition.   The polymer having the carboxy group and the monomer having the glycidyl group and the vinyl group are contained in an amount of 20 to 70% by weight and 0.1 to 2.0% by weight with respect to the three components. The photocurable resin composition as described in any one.   The photocurable resin composition according to any one of claims 1 to 4, wherein the polymer containing a carboxy group has a weight average molecular weight of 30,000 to 350,000. Claims polymer containing the carboxyl group derived from the (meth) acrylic acid, maleic acid, monomers fumaric acid, itaconic acid, Ru is selected from crotonic acid, and allyl carboxylic acids, having a weight average molecular weight of from 30,000 to 350,000 Item 6. The photocurable resin composition according to any one of Items 1 to 5.   The photocurable resin composition according to any one of claims 1 to 6, wherein the monomer having a glycidyl group and a vinyl group is selected from glycidyl (meth) acrylate, allyl glycidyl ether, and hydroxybutyl acrylate glycidyl ether. .   The photocurable resin composition further includes water and an inorganic salt that dissolves in water, and the water and the inorganic salt are 0.1 to 10 parts by weight and 0. The photocurable resin composition according to any one of claims 1 to 7, which is contained in an amount of 003 to 0.1 parts by weight.   An adhesive polymer gel obtained by curing the photocurable resin composition according to any one of claims 1 to 8.