JP2019111660A - Laminate having adhesive layer and method for producing laminate - Google Patents

Abstract

To provide a laminate having an adhesive layer having good adhesion and stress relaxation property.SOLUTION: A laminate has a lamination unit having a transparent resin layer and a glass layer arranged through an adhesive layer. The adhesive layer contains a vinyl polymer (A) and an acrylic adhesive polymer (B), and has a film thickness of 100 μm or more and 5 mm or less. The vinyl polymer (A) has a glass transition temperature (Tg) of 30°C or higher and 200°C or lower and a number average molecular weight of 500-10,000, and is contained in an amount of 0.5 pts.mass or more and 60 pts.mass or less with respect to 100 pts.mass of the acrylic adhesive polymer (B). A second Tg that is a glass transition temperature calculated from the surface layer portion obtained by X-ray photoelectron spectroscopy of the adhesive layer is higher than a first Tg that is a glass transition temperature of the whole adhesive layer by 30°C or higher.SELECTED DRAWING: None

Description

  The present specification relates to a laminate including a pressure-sensitive adhesive layer and a method of manufacturing the laminate.

  In recent years, laminates of plastics such as polycarbonate (PC) resin and acrylic resin and glass have been widely used. Such a configuration of the laminate can improve the performance such as abrasion resistance and chemical resistance as compared with the case of using plastic alone. Moreover, compared with the case where glass is used alone, weight reduction and processability of material can be improved. For this reason, the above-mentioned laminate is applied to various applications such as, for example, a light transmission panel for traffic roads, a simple door, a simple roof such as a terrace or a carport, a solarium, a daylighting window, and a display substrate. ing.

  As such a laminate, for example, Patent Document 1 discloses a light transmission panel for a traffic route formed by bonding a polycarbonate plate between two plate glasses via a resin layer. It is described that this light transmission panel for traffic roads has high durability to impact and penetration while maintaining the aesthetic appearance by such a configuration. Also, for example, Patent Document 2 discloses a laminate in which a plastic film and a glass film are bonded via a resin layer.

JP, 2013-079489, A JP 2001-113631 A

  In each of the applications described above for laminates, it is often used outdoors where there is a large temperature difference, in an automobile where high temperature and high humidity conditions occur, etc. Under such conditions, for example, outgassing generated from plastic substrates And swelling and peeling may occur.

  For this reason, the pressure-sensitive adhesive used to bond the respective substrates of the laminate results from the difference in the thermal expansion coefficient of the respective substrates and the warpage of the resin, in addition to the high adhesiveness and the good transparency to the respective substrates. While relieving stress, high durability without causing any defects is required. Further, from the viewpoint of designability, high heat resistance and moist heat resistance to the laminate are increasing, and a further improvement in performance of the pressure-sensitive adhesive is required. However, no appropriate pressure-sensitive adhesive has been proposed at present.

  The present specification provides a laminate having a pressure-sensitive adhesive layer that can solve the above-mentioned problems, and a method of manufacturing the laminate.

  As a result of intensive investigations in view of the above problems, the present inventors include a low molecular weight vinyl polymer as a tackifier component and an acrylic adhesive polymer as a base polymer component or a polymer syrup for obtaining such a polymer. Attention was focused on the pressure-sensitive adhesive composition. And when forming an adhesive layer with such an adhesive composition, it learned that it could segregate a tackifier component on the surface layer of the adhesive layer. In addition, it was found that by forming a thickened pressure-sensitive adhesive layer with this pressure-sensitive adhesive composition, it is possible to suitably relieve stress while being excellent in heat resistance and moist heat resistance. This specification provides the following means based on such knowledge.

[1] A laminate comprising a lamination unit having a transparent resin layer and a glass layer disposed via an adhesive layer, which is a laminate
The pressure-sensitive adhesive layer contains a vinyl polymer (A) and an acrylic adhesive polymer (B), and has a thickness of 100 μm to 5 mm,
The vinyl polymer (A) has a glass transition temperature (Tg) of 30 ° C. or more and 200 ° C. or less, a number average molecular weight of 500 to 10,000, and 100 parts by mass of the acrylic adhesive polymer (B) To 0.5 parts by mass to 60 parts by mass,
The second Tg, which is the glass transition temperature calculated from the surface layer portion obtained by X-ray photoelectron spectroscopy analysis of the pressure-sensitive adhesive layer, is 30 ° C. or more than the first Tg, which is the glass transition temperature of the entire pressure-sensitive adhesive layer High, laminated.
[2] The laminate according to [1], wherein the first Tg is −80 ° C. or more and 10 ° C. or less.
[3] The laminate according to [1] or [2], wherein the Tg of the vinyl polymer (A) is 60 ° C. or more and 200 ° C. or less.
[4] The laminate according to any one of [1] to [3], wherein the pressure-sensitive adhesive layer further comprises a crosslinking agent.
[5] The pressure-sensitive adhesive sheet having a 100 μm thick polyethylene terephthalate film substrate with the pressure-sensitive adhesive layer having a film thickness of 150 μm at a temperature of 85 ° C. and a peeling speed of 300 mm / min. The laminated body in any one of [1]-[4] whose peeling strength with respect to the glass plate in 85 degreeC and peeling speed 300 mm / min of the said adhesive sheet is 6.0 N / 25 mm or more.
[6] The laminate according to any one of [1] to [5], wherein the acrylic adhesive polymer (B) is formed by polymerizing an acrylic adhesive polymer syrup (C).
[7] It is a manufacturing method of a layered product,
The laminate comprises a lamination unit having a transparent resin layer and a glass layer via an adhesive layer,
The pressure-sensitive adhesive composition described below between the transparent resin layer and the glass layer;
A vinyl polymer (A), an acrylic adhesive polymer syrup (C), and a polymerization initiator, wherein the vinyl polymer (A) has a glass transition temperature (Tg) of 30 ° C. or more and 200 ° C. or less, The number average molecular weight is 500 to 10,000, and the content is 0.5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the acrylic adhesive polymer (B),
Forming the pressure-sensitive adhesive layer by polymerizing the acrylic pressure-sensitive adhesive polymer syrup (C) in to form the laminated unit,
A manufacturing method.

  The present specification relates to a laminate comprising a pressure-sensitive adhesive layer having high adhesiveness and capable of exhibiting excellent heat resistance and stress relaxation, and a method for producing the laminate.

  The pressure-sensitive adhesive layer (hereinafter also referred to as the present pressure-sensitive adhesive layer) having a thickness of 100 μm or more and 5 mm or less disclosed in the present specification is a vinyl polymer (A) having a constant glass transition temperature and a number average molecular weight An acrylic adhesive polymer (B) is contained, and at the time of formation of the present adhesive layer, the vinyl polymer (A) can be segregated to the surface layer of the adhesive layer. By using the present pressure-sensitive adhesive layer, it is possible to obtain a laminate capable of suppressing a decrease in adhesiveness by exhibiting sufficient heat resistance and moist heat resistance under high temperature conditions and high temperature and high humidity conditions. For example, due to use in a high temperature range, floating or peeling of the pressure-sensitive adhesive layer can be suppressed even if outgassing occurs from a lamination target, and good adhesion durability can be exhibited. For this reason, it is possible to obtain a laminate having good durability against thermal expansion and contraction through a high temperature range. Moreover, the said laminated body can be relieve | moderated suitably the stress by the expansion | swelling-shrinkage characteristic from which a different-type base material differs by being equipped with this thick adhesive layer. As a result, the laminated body laminated | stacked through this adhesive layer can be equipped with the outstanding durability.

  The present pressure-sensitive adhesive layer has a sufficiently flexible property as the whole of the pressure-sensitive adhesive layer of the one having the vinyl polymer (A) having a relatively high Tg, and therefore can exhibit a good stress relaxation property. In addition, due to the vinyl polymer (A) segregating on the surface of the pressure-sensitive adhesive layer, high adhesiveness can be exhibited at the interface with the adherend even under high temperature conditions. Therefore, even when exposed to high temperature, it has the property of relieving the stress generated by the difference in the expansion coefficient of the different types of base materials, and the durability is also excellent.

  Incidentally, the segregation behavior of the vinyl polymer (A) to the surface layer of the pressure-sensitive adhesive layer when forming the pressure-sensitive adhesive layer is that the specific vinyl polymer (A) and the acrylic pressure-sensitive adhesive polymer (B) completely Is incompatible, but is not completely phase separated. Preferably, the vinyl polymer (A) is less polar than the acrylic tacky polymer (B).

  For the pressure-sensitive adhesive layer, as described above, a vinyl polymer (A) which is not completely compatible with the acrylic pressure-sensitive adhesive polymer (B) is used. At this time, the degree of segregation can be controlled by appropriately adjusting the amount of the vinyl polymer (A) used in the pressure-sensitive adhesive composition. When the amount of the vinyl polymer (A) used is too small, segregation to the surface layer of the pressure-sensitive adhesive layer may be insufficient and a sufficient effect may not be obtained. On the other hand, when the amount of the vinyl polymer (A) used is too large, phase separation with the acrylic pressure-sensitive adhesive polymer (B) tends to result in deterioration of the transparency and adhesion performance of the pressure-sensitive adhesive layer. In addition, the glass transition temperature of the vinyl polymer (A) and the crosslinking agent are appropriately adjusted, whereby the glass transition temperature of the surface layer portion of the pressure-sensitive adhesive layer can be adjusted.

  Furthermore, such a pressure-sensitive adhesive layer can suppress floating and peeling of the pressure-sensitive adhesive layer even when outgassing from an adherend at high temperature, and can exhibit good adhesion durability.

  Hereinafter, the disclosure of the present specification will be described in detail. In the present specification, "(meth) acrylic" means acrylic and / or methacrylic, and "(meth) acrylate" means acrylate and / or methacrylate. Moreover, "(meth) acryloyl group" means an acryloyl group and / or a methacryloyl group.

  The present pressure-sensitive adhesive layer contains a vinyl polymer (A) and an acrylic adhesive polymer (B). The details of the vinyl polymer (A), the acrylic tacky polymer (B) and the pressure-sensitive adhesive layer containing them will be sequentially described below.

[Vinyl polymer (A)]
The vinyl polymer (A) disclosed in the present specification can be a polymer having a glass transition temperature (Tg) of 30 ° C. or more and 200 ° C. or less. The lower limit of Tg is, for example, 40 ° C. or more, for example, 50 ° C. or more, and for example, 60 ° C. or more, for example, 70 ° C. or more. The upper limit of Tg is, for example, 180 ° C. or less, for example, 150 ° C. or less, and for example, 120 ° C. or less, for example, 110 ° C. or less. Further, the upper limit and the lower limit of the range of Tg can be combined as appropriate, for example, 40 ° C. or more and 180 ° C. or less, and for example 60 ° C. or more and 150 ° C. or less. In the present specification, a value measured at a heating rate of 10 ° C./min by differential scanning calorimetry (DSC) is adopted as Tg. If the Tg is less than 30 ° C., the Tg of the surface layer portion of the pressure-sensitive adhesive layer may not be sufficiently high, and the adhesion strength to various adherends may not be sufficient and the durability may be poor. Further, in general, Tg does not exceed 200 ° C. due to limitations of raw material monomers and the like.

  As a monomer which comprises a vinyl polymer (A), the various vinyl-type unsaturated compound which has radical polymerization property can be used, For example, a (meth) acrylic-acid type compound, an aromatic vinyl compound, unsaturated Carboxylic acid, unsaturated acid anhydride, hydroxyl group-containing unsaturated compound, amino group-containing unsaturated compound, amide group-containing unsaturated compound, alkoxyl group-containing unsaturated compound, cyano group-containing unsaturated compound, nitrile group-containing unsaturated compound And maleimide compounds. These compounds may be used alone or in combination of two or more.

  Among these, from the viewpoint of obtaining appropriate compatibility with the acrylic adhesive polymer, it is preferable to use a (meth) acrylic acid-based compound as a main component. The specific amount of use of the (meth) acrylic acid compound in the entire monomer composition of the vinyl polymer (A) is, for example, in the range of 10% by mass to 100% by mass. For example, it is the range of 30 to 95 mass%. The lower limit of the amount used is, for example, 40% by mass or more, and for example, 50% by mass or more. The upper limit of the amount used is, for example, 90% by mass or less, and for example, 80% by mass or less. The amount used is, for example, in the range of 50% by mass to 90% by mass.

  Examples of (meth) acrylic acid compounds include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, ethylhexyl (meth) acrylate ( (Meth) acrylic acid alkyl esters such as n-dodecyl acrylic acid and n-octadecyl acrylic acid; cyclohexyl (meth) acrylic acid, methyl cyclohexyl (meth) acrylic acid, tert-butyl (meth) acrylic acid Cyclohexyl, (meth) acrylic acid cyclododecyl, (meth) acrylic acid Aliphatic ring vinyl monomers such as bornyl, adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate; phenyl (meth) acrylate, (meth) acrylic acid Aromatic ring system vinyl polymers, such as benzyl, are mentioned. These compounds may be used alone or in combination of two or more.

  Among these, relatively high Tg can be set, and the effect of suppressing the floating and peeling of the pressure-sensitive adhesive sheet is high, and the adhesion to the adherend of the olefin system becomes good, (meth) acrylic acid It is preferable to use an aliphatic cyclic vinyl monomer such as isobornyl, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate and adamantyl (meth) acrylate. The amount of use of such aliphatic cyclic vinyl monomer in the total monomer composition of the vinyl polymer (A) can be appropriately set, and is, for example, 10% by mass or more, and for example, 20% by mass or more. For example, it is 80 mass% or less, and is 70 mass% or less, for example. Furthermore, an aliphatic ring system vinyl monomer can be used, for example in 20 mass% or more and 70 mass% or less of the total monomer composition of a vinyl polymer (A).

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinyltoluene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinylxylene, vinylnaphthalene and the like Can be mentioned. These compounds may be used alone or in combination of two or more. The amount of the aromatic vinyl compound used in the total monomer composition of the vinyl polymer (A) can be set appropriately, but for example, 1% by mass or more with respect to the total constituent monomers of the vinyl polymer (A) It is in the range of 40% by mass or less, for example, in the range of 5% by mass to 30% by mass, and for example in the range of 5% by mass to 20% by mass.

  Examples of unsaturated carboxylic acids include (meth) acrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, cinnamic acid, and monoalkyl esters of unsaturated dicarboxylic acids (maleic acid) And fumaric acid, itaconic acid, citraconic acid, maleic anhydride, itaconic anhydride, monoalkyl esters such as citraconic anhydride, and the like. These compounds may be used alone or in combination of two or more.

  Examples of unsaturated acid anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. These compounds may be used alone or in combination of two or more.

  As the hydroxyl group-containing unsaturated compound, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate Mono (meth) acrylic acid esters of polyalkylene glycols such as 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol, polypropylene glycol, p-hydroxystyrene, m-hydroxystyrene O-hydroxystyrene, p-isopropenyl phenol, m-isopropenyl phenol, o-isopropenyl phenol and the like. These compounds may be used alone or in combination of two or more.

  Examples of the amino group-containing unsaturated compound include dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2- (di-n-propylamino) ethyl acrylate, 2-dimethylaminopropyl (meth) acrylate, 2-diethylaminopropyl (meth) acrylate, 2- (di-n-propyl acrylate) Amino) propyl, 3-dimethylaminopropyl (meth) acrylate, 3-diethylaminopropyl (meth) acrylate, 3- (di-n-propylamino) propyl (meth) acrylate and the like. These compounds may be used alone or in combination of two or more.

  Examples of the amide group-containing unsaturated compound include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-methylol (meth) acrylamide and the like. These compounds may be used alone or in combination of two or more.

  As the alkoxyl group-containing unsaturated compound, for example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (n-propoxy) ethyl (meth) acrylate, (meth) acrylate 2- (n-butoxy) ethyl, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 2- (n-propoxy) propyl (meth) acrylate, 2- (meth) acrylate (N-butoxy) propyl etc. are mentioned. These compounds may be used alone or in combination of two or more.

  As the cyano group-containing unsaturated compound, for example, cyanomethyl (meth) acrylate, 1-cyanoethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, 1-cyanopropyl (meth) acrylate, (meth) acrylic 2-cyanopropyl acid, 3-cyanopropyl (meth) acrylate, 4-cyanobutyl (meth) acrylate, 6-cyanohexyl (meth) acrylate, 2-ethyl-6-cyanohexyl (meth) acrylate, ( There may be mentioned 8-cyanooctyl acrylate and the like. These compounds may be used alone or in combination of two or more.

  Examples of the nitrile group-containing unsaturated compound include (meth) acrylonitrile, ethacrylonitrile, α-ethylacrylonitrile, α-isopropylacrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile and the like. These compounds may be used alone or in combination of two or more.

  Examples of maleimide compounds include maleimide, N-methyl maleimide, N-isopropyl maleimide, N-butyl maleimide, N-dodecyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2, 6- dimethylphenyl) maleimide, N- (2, 6-diethylphenyl) maleimide, N- benzyl maleimide, N- naphthyl maleimide etc. are mentioned. These compounds may be used alone or in combination of two or more.

  Besides the above compounds, dialkyl esters of unsaturated dicarboxylic acids, vinyl ester compounds, vinyl ether compounds and the like can also be used. Examples of dialkyl esters of unsaturated dicarboxylic acids include dialkyl esters such as maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride and the like. Examples of the vinyl ester compound include methylene aliphatic monocarboxylic acid esters, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl butyrate, vinyl benzoate, vinyl formate, vinyl cinnamate and the like. Examples of the vinyl ether compounds include vinyl methyl ether, vinyl ethyl ether, vinyl n-butyl ether, vinyl isobutyl ether, vinyl phenyl ether, vinyl cyclohexyl ether and the like.

  The number average molecular weight (Mn) of the vinyl polymer (A) can be 500 or more and 10,000 or less. For example, it is 500 or more and 7,000 or less, and for example, 1,000 or more and 5,000 or less. When Mn exceeds 10,000, the compatibility with the acrylic tacky polymer (B) is deteriorated. On the other hand, there are problems such as the need for using a large amount of a polymerization initiator and a chain transfer agent, and the decrease in productivity, etc., in order to produce a polymer having an Mn of less than 500.

  Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the above (Mn) is, for example, 3.0 or less from the viewpoint that good adhesive strength is easily obtained. For example, it is 2.5 or less, for example, 2.0 or less, and for example, 1.8 or less. The weight average molecular weight Mw and the number average molecular weight Mn are standard polystyrene equivalent values obtained using gel permeation chromatography (GPC).

  The vinyl polymer (A) is not particularly limited in its production method, but can be easily obtained, for example, by polymerizing the above-mentioned monomers using a known radical polymerization method such as solution polymerization method. . In the case of solution polymerization, an organic solvent and a vinyl monomer raw material are charged in a reactor, and a thermal polymerization initiator such as an organic peroxide or an azo compound is added and copolymerized by heating to 50 to 300 ° C. Thus, the target vinyl polymer can be obtained. The said vinyl polymer may be used as a solution melt | dissolved in the organic solvent, and a solvent may be distilled off and used by a heating pressure reduction process etc., and it may be used.

  The method of preparing each raw material containing a monomer may be a batch-type initial batch charging in which all the raw materials are charged collectively, or a semi-continuous charging in which at least one raw material is continuously fed into the reactor. A continuous polymerization system may be used in which the raw material is continuously supplied and at the same time the product resin is continuously withdrawn from the reactor.

  As the organic solvent used in the solution polymerization method, organic hydrocarbon compounds are suitable, and cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, ethyl acetate and butyl acetate Examples thereof include esters, ketones such as acetone, methyl ethyl ketone and cyclohexanone, alcohols such as methanol, ethanol and isopropanol, methyl orthoformate, methyl ortho acetate and the like, and one or more of these can be used. Among these organic solvents, preferred are ethyl acetate, butyl acetate, acetone and methyl ethyl ketone, which dissolve the vinyl polymer well and have a relatively low boiling point to facilitate purification.

  As the initiator used in the present specification, an azo compound, an organic peroxide, an inorganic peroxide and the like can be used, but it is not particularly limited. You may use the redox type polymerization initiator which consists of a well-known oxidizing agent and a reducing agent. Also, known chain transfer agents can be used in combination.

  As an azo compound, for example, 2,2′-azobis (isobutyronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), azocumene, 2,2′-azobis (2-methylbutyronitrile ), 2,2′-azobisdimethylvaleronitrile, 4,4′-azobis (4-cyanovaleric acid), 2- (tert-butylazo) -2-cyanopropane, 2,2′-azobis (2,4) 2,4-trimethylpentane), 2,2'-azobis (2-methylpropane), dimethyl 2,2'-azobis (2-methylpropionate) and the like.

  As the organic peroxide, for example, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane 1,1-bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, cumene hydroperoxide, 2,5-dimethylhexane-2,5-di Hydroperoxide, 1,3-bis [(tert-butylperoxy) -m-isopropyl] benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, diisopropylbenzene peroxide, tert -Butylcumyl peroxide Decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, bis (tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxybenzoate, 2,5-dimethyl-2,5 -Di (benzoylperoxy) hexane etc. are mentioned.

  As an inorganic peroxide, potassium persulfate, sodium persulfate, ammonium persulfate etc. are mentioned, for example.

  As a redox type polymerization initiator, for example, sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, ferrous sulfate etc. as a reducing agent, potassium peroxodisulfate, hydrogen peroxide, tert-butyl hydroper An oxide using an oxide etc. can be used.

  In order to adjust the molecular weight of the vinyl polymer (A), known chain transfer agents may be used if necessary. As a chain transfer agent, ethanethiol, butanethiol, dodecanethiol, benzenethiol, toluenethiol, α-toluenethiol, phenethyl mercaptan, mercaptoethanol, 3-mercaptopropanol, thioglycerin, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, α-mercaptoisobutyric acid, methyl mercaptopropionate, ethyl mercaptopropionate, thioacetic acid, thiomalic acid, thiosalicylic acid, octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert- tetradecyl mercaptan etc. are mentioned.

  The vinyl polymer (A) can also be obtained by continuous polymerization in a temperature range of 180 to 350 ° C. using a stirred tank reactor. In this polymerization method, since a relatively low molecular weight vinyl polymer can be obtained without substantially using a polymerization initiator or a chain transfer agent, a polymer with high purity is obtained, and the coloration and odor point described later can be obtained. However, it is preferable because it is advantageous. When the polymerization temperature is less than 180 ° C., the polymerization reaction requires a polymerization initiator and a large amount of chain transfer agent, and the obtained copolymer is easily colored and generates an undesirable odor. On the other hand, when the polymerization temperature exceeds 350 ° C., a decomposition reaction is likely to occur during the polymerization reaction, and the resulting copolymer is colored, which may cause a decrease in the transparency of the adhesive layer containing the same. Furthermore, according to such a polymerization method, a vinyl polymer having a small molecular weight distribution range can be obtained. The polymerization initiator may optionally be used, but can be used, for example, at about 1% by mass or less based on all monomers.

[Acryl-based adhesive polymer (B)]
The acrylic adhesive polymer (B) disclosed in the present specification is a polymer containing (meth) acrylic acid esters as a main constituent unit. An acrylic adhesive polymer (B) is a polymer which has adhesiveness whose glass transition temperature (Tg) is in the range of -80 degreeC or more and 10 degrees C or less, for example. The lower limit of Tg is, for example, -70 ° C or more, for example, -60 ° C or more, for example, -50 ° C or more, for example, -40 ° C or more, for example, -30 ° C or more. The upper limit of Tg is, for example, 5 ° C. or less, for example, 1 ° C. or less, for example, 0 ° C. or less, and for example, −10 ° C. or less. In addition, the upper limit and the lower limit of the range of Tg can be combined as appropriate, for example, in the range of -70 ° C to 10 ° C, for example -60 ° C to 10 ° C, for example -50 ° C to 0 ° C. In addition, when Tg is less than -80 degreeC, the cohesion force of the adhesive obtained may become inadequate and there exists a tendency for adhesiveness to deteriorate. When the Tg exceeds 10 ° C., the step conformity and the adhesion at low temperatures may not be sufficient.

  Furthermore, the weight average molecular weight (Mw) of the acrylic adhesive polymer (B) is, for example, 100,000 or more from the viewpoint of exerting sufficient cohesion and good adhesiveness. For example, it is 300,000 or more, for example, 400,000 or more, and can be 500,000 or more, for example. The weight average molecular weight is preferably 600,000 or more in that the heat resistance is further improved. For example, 700,000 or more, such as 800,000 or more, such as 900,000 or more, such as 1,000,000. The above can also be made. On the other hand, when the weight-average molecular weight is too large, the step following property tends to be reduced, which may make it difficult to handle in production. Therefore, the upper limit value is, for example, 5,000,000 or less. For example, it can be 3,000,000 or less, for example 2,000,000 or less, or for example 1,000,000 or less.

  Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the above (Mn) is, for example, 6.0 or less from the viewpoint that a favorable adhesive strength is easily obtained. For example, it is 5.0 or less, for example, 4.7 or less, and for example, 4.5 or less, and for example, 4.0 or less, for example, 3.8 or less, for example, 3.6 or less, etc. It can also be done. The weight average molecular weight Mw and the number average molecular weight Mn are standard polystyrene equivalent values obtained using gel permeation chromatography (GPC).

  As a monomer constituting the acrylic adhesive polymer (B), an alkyl (meth) acrylate having an alkyl group having 1 to 12 carbon atoms in that an acrylic copolymer having a low Tg and adhesiveness is obtained. Examples thereof include esters and (meth) acrylic acid alkoxyalkyl esters having an alkoxyalkyl group having 2 to 12 carbon atoms, and one or more of them can be used.

  As the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate N-Butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate And (meth) acrylic acid n-nonyl, (meth) acrylic acid isononyl, (meth) acrylic acid n-decyl, (meth) acrylic acid lauryl and the like, and preferred monomers include (meth) acrylic acid n- Butyl, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acrylate i Octyl, (meth) acrylic acid n- nonyl include isononyl (meth) acrylic acid.

  As the (meth) acrylic acid alkoxyalkyl ester having an alkoxyalkyl group having 2 to 12 carbon atoms, for example, methoxymethyl (meth) acrylate, ethoxymethyl (meth) acrylate, butoxymethyl (meth) acrylate, (meth) Examples thereof include methoxyethyl acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, ethoxybutyl (meth) acrylate, butoxybutyl (meth) acrylate and the like.

  The amount of the (meth) acrylic acid alkyl ester having a C 1-12 alkyl group and / or the (meth) acrylic acid alkoxyalkyl ester having a C 2-12 alkoxyalkyl group is not particularly limited. However, the lower limit thereof can be 10% by mass or more based on the total constituent monomers of the acrylic copolymer, in a point that good adhesion performance tends to be obtained, for example, 15% by mass More, for example, 20 mass% or more, for example 25 mass% or more, for example 30 mass% or more, for example 40 mass% or more, for example 50 mass% or more, for example 60 mass% or more, for example 70 mass% or more Also, it can be, for example, 80% by mass or more, for example, 90% by mass or more. The upper limit thereof is 100% by mass or less, and may be 99% by mass, for example, 95% by mass or less, for example 90% by mass or less, for example 80% by mass or less, for example 70% by mass The following can be done. Although the range of the amount used can be set by combining these upper and lower limits as appropriate, it is, for example, 10% by mass or more and 95% by mass or less, for example, 20% by mass or more and 95% by mass or less, for example, 30% by mass or more and 70% by mass Or less, for example, 40% by mass or more and 60% by mass or less

  In addition, from the viewpoint that the vinyl polymer (A) is easily segregated in the surface layer of the obtained pressure-sensitive adhesive layer, an alkoxyalkyl group having 2 to 4 carbon atoms is added to all monomer units constituting the acrylic copolymer. 10 mass% or more of at least 1 sort (s) of compounds chosen from the group which consists of (meth) acrylic-acid alkoxy alkyl ester which has, and a (meth) acrylic-acid alkyl ester which has a C1-C4 alkyl group can be included. For example, the lower limit is 15% by mass or more of all monomer units, for example 20% by mass or more, for example 25% by mass or more, for example 30% by mass or more, for example 35% by mass or more, for example 40% by mass As described above, for example, 50% by mass or more, for example, 60% by mass or more, for example, 70% by mass or more, for example, 80% by mass or more, for example, 90% by mass or more. The upper limit thereof may be, for example, 99% by mass, and may be, for example, 95% by mass or less, for example, 90% by mass or less, for example, 80% by mass or less, for example, 70% by mass or less. The range of the amount used can be set by combining these upper and lower limits as appropriate, for example, 10 to 99 mass%, for example, 20 to 95 mass%, for example, 20 to 85 mass%. Hereinafter, for example, it can be 20 mass% or more and 70 mass% or less, for example, 30 mass% or more and 60 mass% or less.

  The acrylic adhesive polymer (B) is not limited to the above (meth) acrylic acid alkyl ester and (meth) acrylic acid alkoxy alkyl ester, but other single units copolymerizable therewith as long as the tackiness is not impaired You can use the body.

  As other vinyl monomers, for example, α, β-ethylenically unsaturated carboxylic acid monomers such as (meth) acrylic acid, itaconic acid, maleic acid and fumaric acid; styrene, α-methylstyrene, vinyl Aromatic vinyl monomers such as toluene; cyclohexyl (meth) acrylate, methyl cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, isobornyl (meth) acrylate Aliphatic ring vinyl monomers such as: monoalkyl esters of unsaturated dicarboxylic acids such as itaconic acid monoethyl ester and fumaric acid monobutyl ester; 2-hydroxyethyl (meth) acrylate, 3- (meth) acrylic acid Hydroxypropyl, 4-hydroxybutyl (meth) acrylate, polyethylene glycol (Meth) acrylate, polypropylene glycol (meth) acrylate, and hydroxyl group-containing monomer such as polyethylene-polypropylene glycol mono (meth) acrylate; ethylene such as acrylamide, N-methylol acrylamide, N-methoxymethyl acrylamide, N-methoxybutyl acrylamide And N-substituted compounds; unsaturated alcohols such as allyl alcohol; (meth) acrylonitrile, vinyl acetate, glycidyl (meth) acrylate, diacetone acrylamide and the like, and one or more of them may be mentioned. Two or more types can be used.

  In addition, you may use the polyfunctional polymerizable monomer which has 2 or more of polymerizable functional groups, such as a (meth) acryloyl group and an alkenyl group, in a molecule | numerator. A polyfunctional polymerizable monomer acts as a so-called crosslinking agent, and by using this, a crosslinked structure can be formed in the present adhesive polymer.

  As polyfunctional (meth) acrylate compounds, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol Di) (meth) acrylates of dihydric alcohols such as meta) acrylate; trimethylolpropane tri (meth) acrylate, tri (meth) acrylate of trimethylol propane ethylene oxide modified product, glycerin tri (meth) acrylate, pentaerythritol tri ( Poly (meth) acrylates such as tri (meth) acrylates and tetra (meth) acrylates of trivalent or higher polyhydric alcohols such as meta) acrylate and pentaerythritol tetra (meth) acrylate Mention may be made of the rate, and the like.

  As polyfunctional alkenyl compounds, polyfunctional allyl ether compounds such as trimethylolpropane diallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, tetraallyloxy ethane, polyallyl saccharose; polyfunctional allyl compounds such as diallyl phthalate; methylene Examples thereof include bisamides such as bisacrylamide and hydroxyethylene bisacrylamide; and polyfunctional vinyl compounds such as divinylbenzene.

  Examples of compounds having both (meth) acryloyl group and alkenyl group include allyl (meth) acrylate, isopropenyl (meth) acrylate, butenyl (meth) acrylate, pentenyl (meth) acrylate, (meth) acrylic acid 2- (2-vinyloxyethoxy) ethyl etc. can be mentioned.

  The acrylic adhesive polymer (B) can also be obtained by a known radical polymerization method such as a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method.

[Acrylic sticky polymer syrup (C)]
The acrylic sticky polymer syrup (C) (hereinafter also referred to as the present syrup) is a polymer syrup from which the above-mentioned acrylic sticky polymer (B) can be obtained. In the present specification, the syrup contains a polymer component that is a part of the acrylic adhesive polymer (B) and a (meth) acrylic monomer that constitutes the remainder of the acrylic adhesive polymer (B). Can.

  This syrup is a polymer syrup from which it is possible to obtain an acrylic adhesive polymer (B). In the present specification, the syrup may contain a polymer component which is a part of the above-mentioned acrylic adhesive polymer (B) and a monomer component for constituting the remainder of the acrylic adhesive polymer (B). it can. More specifically, the syrup may be a mixture of polymer component / monomer component obtained by partially polymerizing all the monomers constituting the acrylic adhesive polymer (B), It may be a polymer component / monomer component obtained by adding a monomer of type B. Furthermore, it may be a mixture of a polymer component / monomer component obtained by obtaining a polymer component in advance by a known polymerization method and adding a predetermined monomer thereto.

  The syrup is a mixture of polymer component / monomer component, but can generally take the form of a solution in which the polymer component is dissolved in the remaining monomer. Since the polymer component and the residual monomer are liquid, the vinyl polymer (A) is dissolved until just before the polymerization of this syrup, while the tackifier component is formed as the acrylic adhesive polymer (B) is polymerized. The vinyl polymer (A) can be segregated in the surface layer of the pressure-sensitive adhesive layer.

  The constituent monomers of the polymer component contained in the syrup and the remaining monomers may use one or more of the same monomers or may be different, but preferably one or more of them Use the same monomers of When the monomer is the same, the compatibility of the polymer component with the remaining monomer is excellent, and the transparency when the pressure-sensitive adhesive layer is formed is excellent. The use of one or two or more identical monomers means at least the same monomer composition from the viewpoint of the type of monomers, and preferably also the same monomer composition in quantitative terms. doing.

  The ratio of the polymer component to the residual monomer in the syrup is not particularly limited as long as the viscosity necessary for the formation and handling of the coating film can be obtained. For example, the polymer component is 1% by mass or more and 99% by mass or less and the balance is the remaining monomer. Also, for example, the polymer component is 10% by mass or more and 90% by mass or less, and the balance is the remaining monomer. Also, for example, the polymer component is 20% by mass or more and 80% by mass or less, and the balance is the remaining monomer. Also, for example, the polymer component is 30% by mass or more and 70% by mass or less, and the balance is the remaining monomer.

  The polymer component has, for example, a number average molecular weight (Mn) of 50,000 or more, such as 100,000 or more, such as 120,000 or more, such as 130, from the viewpoint of exhibiting sufficient cohesion and good adhesion. Or more, for example, 140,000 or more, or for example, 150,000 or more. On the other hand, when the number average molecular weight is too high, handling in production may be difficult. Therefore, the upper limit can be, for example, 500,000 or less, for example, 400,000 or less, or for example, 300,000 or less, or for example, 200,000 or less.

  The weight average molecular weight (Mw) of the polymer component can be, for example, 300,000 or more, for example, 400,000 or more, for example, 500,000 or more, from the viewpoint of imparting good cohesion. Further, a weight average molecular weight (Mw) of 600,000 or more is preferable in that the heat resistance is further improved. For example, 700,000 or more, for example, 800,000 or more, for example, 900,000 or more, for example 1,1 or more. It is also possible to set it as 000 000 or more. On the other hand, when the weight average molecular weight is too high, handling in production may be difficult. Therefore, the upper limit can be, for example, 3,000,000 or less, or, for example, 2,000,000 or less, or, for example, 1,000,000 or less.

  The polymer component contained in the syrup can be obtained by a known radical polymerization method such as bulk polymerization method, solution polymerization method, suspension polymerization method, emulsion polymerization method and the like. In addition to the necessary monomers, a polymerization initiator, a polymerization regulator and a chain transfer agent can be used in the polymerization.

  As the polymerization initiator, various known polymerization initiators such as thermal decomposition type and photo initiation type can be used. Preferably, a photoinitiator is used.

  As organic peroxides which are thermal decomposition type polymerization initiators, for example, dicumyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, diacetyl peroxide And didecanoyl peroxide, diisononoyl peroxide, 2-methylpentanoyl peroxide and the like. Further, as organic hydroperoxides, tert-butyl hydroperoxide, cumyl hydroperoxide, 2,5-dimethyl-2,5-dihydroperoxyhexane, p-methane hydroperoxide, diisopropylbenzene hydroperoxide -An oxide etc. can be illustrated.

  As organic peroxides that are thermal decomposition type polymerization initiators, 1,1-bis (tert-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-hexylperone) Oxy) cyclohexane, 1,1-bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane, and as azo compounds, 2,2'-azobisisobutyronitrile, 2,2'-azobis -2,4-Dimethylvaleronitrile, 2,2'-azobiscyclohexyl nitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2-phenylazo-4-methoxy-2,4-dimethyl valeronitrile, Dimethyl-2,2'-azobisisobutyrate etc. can be illustrated respectively.

  Examples of the photopolymerization initiator include benzoin and its alkyl ethers, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, xanthones, acyl phosphine oxides, α-diketones and the like.

  These polymerization initiators can be used in the range of 0.0001 to 0.5 parts by mass with respect to 100 parts by mass of the mixture of monomers for obtaining the acrylic adhesive polymer (B).

  As described above, in the present syrup, the above polymerization initiator is added to the monomer for constituting the acrylic adhesive polymer (B), and the monomer is partially polymerized to obtain a polymer component, or an acrylic adhesive The polymer component obtained by polymerizing a part of the monomers for constituting the polymer (B) is obtained by dissolving it in the remaining monomers other than the part of the monomers.

[Pressure-sensitive adhesive composition]
The pressure-sensitive adhesive composition (hereinafter also referred to as the present pressure-sensitive adhesive composition) for obtaining the present pressure-sensitive adhesive layer comprises a vinyl polymer (A) and an acrylic tacky polymer (B) or an acrylic tacky polymer syrup ( C) and can be contained. When the pressure-sensitive adhesive composition contains an acrylic adhesive polymer syrup (C), it can further contain a polymerization initiator.

  The vinyl polymer (A) has appropriate compatibility with the acrylic adhesive polymer (B) and the acrylic adhesive polymer syrup (C). For this reason, the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition containing them exhibits good transparency, and the vinyl polymer (A) is partially segregated in the pressure-sensitive adhesive layer, and the vinyl polymer (the surface layer portion The concentration of A) may be higher than other parts.

  As described above, when the concentration of the vinyl polymer (A) in the surface layer portion of the pressure-sensitive adhesive layer is higher than the other, even in the case of a laminate in which the pressure-sensitive adhesive sheet is attached to the transparent plastic substrate, Since the pressure-sensitive adhesive layer has a relatively high Tg, it can exhibit good adhesion even under high temperature conditions. In addition, floating and peeling of the pressure-sensitive adhesive sheet due to the outgas generated from the adherend are suppressed. Furthermore, since the pressure-sensitive adhesive layer as a whole has a low Tg and is sufficiently flexible, the thickened pressure-sensitive adhesive layer follows the expansion and contraction of various substrates, and the stress resulting from the difference in thermal expansion coefficient is It can be relaxed suitably.

  In addition to the segregation behavior of the vinyl polymer (A) in the pressure-sensitive adhesive composition, the difference in Tg between the surface layer portion of the pressure-sensitive adhesive layer described later and the entire pressure-sensitive adhesive layer is the acrylic adhesive polymer (B) and the acrylic adhesive Composition ratio of vinyl polymer (A) to water soluble polymer syrup (C), monomer composition (polarity) and molecular weight of vinyl polymer (A), and adjustment by appropriately setting Tg, Mw / Mn, etc. be able to.

  The present pressure-sensitive adhesive composition can contain the vinyl polymer (A) in an amount of 0.5 parts by mass or more and 60 parts by mass or less based on 100 parts by mass of the acrylic adhesive polymer (B) in terms of solid content. Similarly, in the present pressure-sensitive adhesive composition, the vinyl polymer (A) is contained in an amount of 0.5 parts by mass or more and 60 parts by mass or less based on 100 parts by mass of the acrylic adhesive polymer syrup (C) in terms of solid content. It can be contained. The lower limit of the content is, for example, 1 part by mass or more, for example, 3 parts by mass or more, and for example, 4 parts by mass or more. The upper limit of the content is, for example, 50 parts by mass or less, for example, 40 parts by mass or less, and for example, 30 parts by mass or less. Moreover, the range of content is, for example, 1 part by mass or more and 40 parts by mass or less, and for example, 3 parts by mass or more and 30 parts by mass or less. When the amount of the vinyl polymer (A) used is less than 0.5 parts by mass, segregation of the vinyl polymer (A) in the pressure-sensitive adhesive layer is insufficient, and particularly satisfactory results in high-temperature adhesion can not be obtained. There is. On the other hand, when it exceeds 60 parts by mass, the vinyl polymer (A) is excessively segregated, and as a result, the adhesiveness including the step difference and the initial adhesion (tack) may be insufficient. Moreover, it may phase-separate with an acrylic adhesive polymer (B) and an acrylic adhesive polymer syrup (C), and the transparency of an adhesive layer may fall.

  When the pressure-sensitive adhesive composition contains a polymerization initiator (that is, when the pressure-sensitive adhesive composition contains an acrylic adhesive polymer syrup (C)), the polymerization initiator is an acrylic adhesive polymer syrup (C) Various known polymerization initiators such as thermal decomposition type, photo initiation type and the like similar to those which can be used in the present invention can be used. Preferably, a photoinitiator is used. In addition, in order to improve the sensitivity to the active energy ray irradiated for the polymerization of the acrylic adhesive polymer syrup (C), benzoic acid-based and amine-based photosensitizers can also be used as needed. .

  In the pressure-sensitive adhesive composition, the polymerization initiator can be used, for example, about 0.01 parts by mass or more and about 10 parts by mass or less with respect to 100 parts by mass of the acrylic adhesive polymer syrup (C). About 05 mass parts or more and 1 mass part or less can be used.

  When the pressure-sensitive adhesive composition contains a vinyl polymer (A) and an acrylic tacky polymer (B), it generally contains an organic solvent etc., but the vinyl polymer (A) and the acrylic tackiness When the polymer syrup (C) is contained, it can be used as a non-solvent type containing no solvents.

  This pressure-sensitive adhesive composition is particularly limited in the mixing method as long as it contains a specified amount of a vinyl polymer (A) and an acrylic adhesive polymer (B) or an acrylic adhesive polymer syrup (C). There is no. For example, the present pressure-sensitive adhesive composition may be obtained by mixing a vinyl polymer (A) and an acrylic tacky polymer (B) or an acrylic tacky polymer syrup (C), or a vinyl polymer ( The present pressure-sensitive adhesive composition may be obtained by polymerizing a predetermined monomer component in the presence of A) to obtain an acrylic adhesive polymer (B) or an acrylic adhesive polymer syrup (C).

  For example, when the pressure-sensitive adhesive composition contains a vinyl polymer (A) and an acrylic adhesive polymer (B), the polymer solution is prepared by dissolving the vinyl polymer (A) in a solvent such as ethyl acetate. While preparing, the polymer solution of acrylic adhesive polymer (B) can be mixed with this polymer solution, and also a crosslinking agent can be mixed as needed, and this adhesive composition can be manufactured.

[Crosslinking agent]
The pressure-sensitive adhesive composition can contain a crosslinking agent. The addition of the crosslinking agent is considered depending on the intended adhesive properties as well as depending on the form of the pressure-sensitive adhesive composition, for example, the form of an emulsion or a solution, etc., although it is not always necessary. By containing a crosslinking agent, the cohesion and adhesion of the pressure-sensitive adhesive layer obtained from the present pressure-sensitive adhesive composition are adjusted, and further, the adhesion under high temperature and high humidity and the adhesion to a curved surface are imparted. be able to. As a crosslinking agent, epoxy compounds having two or more epoxy groups, isocyanate compounds having two or more isocyanate groups, aziridine compounds having two or more aziridinyl groups, oxazoline compounds having oxazoline groups, metal chelate compounds, butylated melamine compounds Etc. Among these, it is preferable to use an aziridine compound, a glycidyl compound and an isocyanate compound.

  Examples of the aziridine compound include 1,6-bis (1-aziridinylcarbonylamino) hexane, 1,1 ′-(methylene-di-p-phenylene) bis-3,3-aziridyl urea, 1,1 ′. -(Hexamethylene) bis-3,3-aziridyl urea, ethylene bis- (2-aziridinyl propionate), tris (1-aziridinyl) phosphine oxide, 2,4,6-triaziridinyl-1,3,5 -Triazine, trimethylolpropane-tris-(2-aziridinyl propionate), etc. are mentioned.

  As an epoxy compound, for example, epoxy resin of bisphenol A epichlorohydrin type, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl Ether, 1,6-hexanediol diglycidyl ether, diglycidyl aniline, tetraglycidyl xylene diamine, N 1, N 2, N ′, N′-tetraglycidyl-m-xylylene diamine, 1,3-bis (N, N- Diglycidylaminomethyl) cyclohexane, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol poly Glycidyl ethers, polyfunctional glycidyl compounds such as sorbitol polyglycidyl ether.

  As an isocyanate compound, preferably, a compound having two or more isocyanate groups is used. As the isocyanate compound, various isocyanate compounds of aromatic type, aliphatic type, and alicyclic type, and modified products (prepolymers etc.) of these isocyanate compounds can be used.

  As aromatic isocyanate, for example, diphenylmethane diisocyanate (MDI), crude diphenylmethane diisocyanate, tolylene diisocyanate, naphthalene diisocyanate (NDI), p-phenylene diisocyanate (PPDI), xylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI) , Tolidine diisocyanate (TODI) and the like. Examples of aliphatic isocyanates include hexamethylene diisocyanate (HDI), lysine diisocyanate (LDI), lysine triisocyanate (LTI) and the like. Examples of alicyclic isocyanates include isophorone diisocyanate (IPDI), cyclohexyl diisocyanate (CHDI), hydrogenated XDI (H6 XDI), hydrogenated MDI (H12 MDI) and the like. Further, as the modified isocyanate, urethane modified body, dimer, trimer, carbodiimide modified body, allophanate modified body, biuret modified body, urea modified body, isocyanurate modified body, oxazolidone modified body, isocyanate of the above isocyanate compound A group terminal prepolymer etc. are mentioned.

  The content of the crosslinking agent can be, for example, 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the acrylic adhesive polymer (B) or the acrylic adhesive polymer syrup (C). The lower limit thereof is, for example, 0.03 parts by mass or more, and for example, 0.05 parts by mass or more. The upper limit thereof is, for example, 5 parts by mass or less, and for example, 2 parts by mass or less. Moreover, the range is, for example, 0.03 parts by mass or more and 5 parts by mass or less, and for example, 0.05 parts by mass or more and 2 parts by mass or less.

[Method of producing the present laminate]
In the case where the present pressure-sensitive adhesive composition contains a vinyl polymer (A) and an acrylic adhesive polymer (B), the present laminate is dried after the pressure-sensitive adhesive composition dissolved in an organic solvent or the like is applied to a separator It can be obtained by Moreover, when this adhesive composition contains a vinyl polymer (A) and an acrylic adhesive polymer syrup (C), after apply | coating the said adhesive composition to a separator, active energy rays, such as UV, are irradiated. It can be obtained by polymerizing the acrylic sticky polymer syrup (C). In the case of the latter, since the foaming associated with the drying process for distilling off the solvent does not occur, the thickening of the pressure-sensitive adhesive layer can be easily performed.

  Segregation of the vinyl polymer (A) occurs when the pressure-sensitive adhesive layer is formed, and the surface layer side (with the evaporation of the solvent or with the polymerization of the acrylic adhesive polymer syrup (C) The vinyl polymer (A) is segregated on the air interface side). Therefore, for example, in a sheet-like or film-like pressure-sensitive adhesive layer of the pressure-sensitive adhesive composition, when two surface layers facing in the thickness direction are in contact with a substance having low surface energy such as gas or certain solid, such substance The pressure-sensitive adhesive layer containing a vinyl polymer (A) at a higher concentration on the low surface energy interface side in contact with the other, and a lower concentration of the vinyl polymer (A) on the center side in the thickness direction of the pressure-sensitive adhesive layer You can get it. That is, it is possible to obtain a pressure-sensitive adhesive layer having a gradient composition having a vinyl polymer (A) at a higher concentration on the surface layer side of the pressure-sensitive adhesive layer. From the viewpoint of the acrylic adhesive polymer (B), it is possible to obtain an adhesive layer having a gradient composition having a lower concentration of the acrylic adhesive polymer (B) on the surface side of the adhesive layer.

  In addition, for example, when only one of two surface layers facing in the thickness direction in the sheet-like or film-like pressure-sensitive adhesive layer of the present pressure-sensitive adhesive composition is on the low surface energy interface side, vinyl weight on the interface side It is possible to obtain a pressure-sensitive adhesive layer containing the combined (A) at a higher concentration.

[Tg of the entire pressure-sensitive adhesive layer (first Tg)]
The glass transition temperature (Tg) of the entire pressure-sensitive adhesive layer, that is, the first Tg can be in the range of −80 ° C. or more and 10 ° C. or less. The lower limit of the first Tg is, for example, -70 ° C or more, for example, -60 ° C or more, for example, -40 ° C or more, and for example, -30 ° C or more. The upper limit of the first Tg is, for example, 0 ° C. or less, for example, −10 ° C. or less, and for example, −20 ° C. or less. Moreover, the range of 1st Tg is -70 degreeC or more and -20 degreeC or less, for example. If the first Tg is less than -80 ° C, the cohesion of the obtained adhesive tends to be insufficient, and the adhesiveness etc. tends to deteriorate, and if it exceeds 10 ° C, the step conformity and low temperature conditions In some cases, the adhesive strength of the The Tg of the pressure-sensitive adhesive composition can be obtained by DSC using a temperature rising rate of 10 ° C./min and a nitrogen atmosphere as a measurement atmosphere.

[Tg (second Tg) calculated from the composition of the surface layer portion of the pressure-sensitive adhesive layer]
The second Tg of the pressure-sensitive adhesive layer, that is, when the pressure-sensitive adhesive layer is obtained by drying or irradiation with active energy rays after applying the pressure-sensitive adhesive composition to a separator, X-ray photoelectron spectroscopy of the pressure-sensitive adhesive layer The Tg calculated from the composition of the surface layer portion obtained by analysis is calculated from the composition ratio of the vinyl polymer (A) and the acrylic adhesive polymer (B) obtained from X-ray photoelectron spectroscopy (XPS) It can be grasped as Tg of the composition which forms the surface layer from the surface of the pressure-sensitive adhesive layer to the depth of about 5 nm. The details of the measurement method can follow the procedure described in the examples below. In the present specification, the surface layer portion means a surface layer portion on the side in contact with each member constituting the laminate.

  The second Tg is not particularly limited, and is, for example, 0 ° C. or more. For example, it is 10 ° C. or more, for example 30 ° C. or more, for example 40 ° C. or more, for example 50 ° C. or more, for example 60 ° C. or more. In addition, 2nd Tg can be suitably adjusted with Tg, a compounding ratio, etc. of a vinyl polymer (A).

[Difference between first Tg and second Tg]
In the pressure-sensitive adhesive layer, the second Tg (Tg calculated from the composition of the surface layer portion of the pressure-sensitive adhesive layer) is 30 ° C. or more higher than the first Tg (Tg of the entire pressure-sensitive adhesive layer) preferable. According to the pressure-sensitive adhesive layer having such a Tg composition, the higher the temperature of the pressure-sensitive adhesive layer formed by the conventional general pressure-sensitive adhesive, the lower the adhesiveness, but the higher the adhesiveness (the peeling to the adherend) Strength) and high stress relaxation properties can be exhibited.

  Furthermore, when the second Tg is higher by 30 ° C. or more than the first Tg, even when transparent plastic substrates such as polypropylene and polycarbonate are used as adherends and this is exposed to high temperature and high humidity Lifting or peeling at the adhesive interface with the pressure-sensitive adhesive layer due to air bubbles (foaming) generated from a plastic substrate or the like is suppressed, and good durability (foaming resistance) is exhibited.

  The second Tg is higher than the first Tg by, for example, 40 ° C. or more, for example, 50 ° C. or more, for example, 60 ° C. or more, for example, 65 ° C. or more, for example, 70 ° C. or more, for example 80 Higher than ° C. The upper limit of the height of the first Tg relative to the second Tg is not particularly limited, but the upper limit is 230 ° C. from the values that the first Tg and the second Tg can take, generally 200 ° C. It is below.

[Mass fraction (A / A + B) of vinyl polymer (A) to the total mass of vinyl polymer (A) and acrylic adhesive polymer (B) in the surface layer portion of the pressure-sensitive adhesive layer]
In the measurement of the second Tg, the composition analysis of the surface layer of the present pressure-sensitive adhesive layer is performed by X-ray photoelectron spectroscopy, and at that time, the mass fraction of the vinyl polymer (A) in the surface layer can be determined. This mass fraction can be used as an indicator of the segregated state of the vinyl polymer (A) in the surface layer portion of the present pressure-sensitive adhesive layer.

  For example, the mass fraction is, for example, 55% or more and 95% or less. The segregation to the surface layer part of a vinyl polymer (A) has arisen as it is this range, and the adhesiveness and stress relaxation property with respect to various base materials can be obtained. The mass fraction is, for example, 60% or more, for example 65% or more, for example 70% or more, for example 75% or more, for example 80% or more, for example 85% or more It is. Also, the mass fraction is, for example, 90% or less.

[Adhesiveness (Peeling strength)]
The pressure-sensitive adhesive layer is a pressure-sensitive adhesive sheet provided with a pressure-sensitive adhesive layer having a film thickness of 150 μm made of the pressure-sensitive adhesive composition on a 100 μm polyethylene terephthalate film (PET) substrate. The peel strength to the plate and the glass plate is, for example, 8.0 N / 25 mm or more and 6.0 N / mm or more, respectively. By providing such adhesive strength, floating and peeling of the pressure-sensitive adhesive sheet can be suppressed with respect to a PC plate and a glass plate exposed to thermal expansion and contraction through a high temperature region. For example, all are 10 N / 25 mm or more, for example, all are 13 N / 25 mm or more, for example, all are 15 N / 25 mm or more.

  Here, in preparing the above-mentioned pressure-sensitive adhesive sheet, a method of obtaining a pressure-sensitive adhesive sheet by directly applying the pressure-sensitive adhesive composition to a polyester film substrate and drying or acting as a polymerization initiator for polymerization and curing After coating on a release paper or the like to form a pressure-sensitive adhesive layer, any method of transferring to a polyester film substrate may be adopted. Drying may be performed at normal temperature, but from the viewpoint of productivity etc., usually, it takes a few seconds to several tens of minutes under heating conditions of 40 to 150 ° C. using a dryer. The method of drying is common. More specifically, when the pressure-sensitive adhesive composition is applied to a PET film separator so that the thickness after drying is 100 μm, after being dried at 60 ° C. for 2 minutes, it is further dried at 80 ° C. for 4 minutes In addition to removing ethyl acetate, cross-linking reaction is performed as needed, and a 50 μm-thick PET separator with different peel strength is attached to the separator, and left at 40 ° C. for 5 days. The adhesive film sample for attached peeling strength measurement can be obtained. In addition, drying conditions can be suitably adjusted with the thickness of the adhesive layer to coat.

  In the measurement of peel strength, this adhesive film sample is further transferred to a PET film (100 μm) subjected to easy adhesion treatment to obtain an adhesive sheet for evaluation, and a PC plate (manufactured by Mitsubishi Gas Chemical Co., Ltd., Iupiron NF 2000, 1. A pressure-sensitive adhesive sheet is attached to a thickness of 5 mm) or a glass plate (manufactured by Asahi Glass Co., Ltd., Fabrytech FL 11A, 1 mm thickness), and 0.5 MPa at 50 ° C. After pressure bonding for 20 minutes under the conditions of, for example, JIS Z-0237 “adhesive tape / adhesive sheet test method under conditions of 23 ° C. using a tensile tester Strograph R type (made by Toyo Seiki Co., Ltd.) with a thermostat The 180-degree peel strength of the pressure-sensitive adhesive sheet can be measured in accordance with the above, and the adhesive strength can be obtained.

  As described above, the present pressure-sensitive adhesive layer can have high adhesiveness to polycarbonate and a glass plate as an adherend at high temperatures, but such properties are based on the Tg composition (distribution) of the pressure-sensitive adhesive layer Therefore, the above-described characteristics can be exhibited with respect to various resins and various glasses other than polycarbonate.

[Transparency (Haze value)]
A haze value can be used as a parameter | index which evaluates the transparency of this adhesive layer. Since the vinyl polymer (A) has appropriate compatibility with the acrylic adhesive polymer (B) or the acrylic adhesive polymer syrup (C) as described above, the adhesive layer of the present adhesive layer contains an adhesive The agent layer exhibits good transparency.

  The haze value can be evaluated, for example, by the following method. That is, after peeling off one separator from the adhesive film sample by this adhesive composition and transferring to a glass plate and peeling off the other separator, it is allowed to stand at 23 ° C., 50% RH for 1 day, and the haze meter is Use to measure haze value. It can be evaluated that the transparency is better as the haze value is lower. The haze value is, for example, 2.0 or less. When the haze value is 2.0 or less, it can be said that there is a certain preferable transparency. The haze value is also, for example, 1.5 or less, for example, 1.2 or less, and for example, 1.0 or less, and for example, 0.8 or less.

[Laminate]
The laminate disclosed in the present specification (hereinafter, also referred to as the present laminate) is a laminate unit having a transparent resin layer and a glass layer disposed via the present pressure-sensitive adhesive layer obtained from the present pressure-sensitive adhesive composition. It can be equipped. The present pressure-sensitive adhesive composition is suitable for bonding different materials as a pressure-sensitive adhesive layer, and a laminate having practical adhesion, heat resistance and stress relaxation can be obtained.

  The thickness (film thickness) of the pressure-sensitive adhesive layer included in the laminate is appropriately selected depending on the application, but is, for example, 50 μm to 10 mm, for example, 100 μm to 10 mm, and for example, 100 μm to 5 mm, For example, it is 150 μm to 5 mm, for example, 200 μm to 3 mm, for example, 250 μm to 3 mm, and for example, 300 μm to 2 mm, and for example, 350 μm to 2 mm. According to the pressure-sensitive adhesive composition, the tackifier component is segregated in the surface layer in response to such thickening easily, and a pressure-sensitive adhesive layer excellent in adhesion, heat resistance and stress relaxation property is formed. it can.

  The laminate has a pressure-sensitive adhesive layer of 100 μm or more under high temperature and high humidity conditions (for example, 60 ° C., 90% RH, 500 hours) and thermal cycle conditions (for example, −20 ° C. and 80 ° C., temperatures 30) It can exhibit excellent durability (peel resistance) in 20 cycles per minute. Moreover, in addition to such high temperature and high humidity conditions and thermal cycle conditions that the film thickness of the adhesive layer is 150 μm or more, excellent durability (peel resistance) even under high temperature conditions (for example, 90 ° C., 500 hours) Can be shown.

  When the pressure-sensitive adhesive layer is 300 μm or more, the laminate can stably exhibit durability under high temperature conditions, high temperature high humidity conditions, and thermal cycle conditions.

  When the film thickness is larger, that is, for example, 150 μm or more, for example, 300 μm or more, it is advantageous to form a film using the acrylic adhesive polymer syrup (C) and the polymerization initiator.

  In the production of a laminate comprising the pressure-sensitive adhesive layer, when the pressure-sensitive adhesive composition contains a vinyl polymer (A) and an acrylic pressure-sensitive adhesive polymer (B), the pressure-sensitive adhesive composition comprises various substrates. After coating on one side or both sides, drying is performed to form a pressure-sensitive adhesive layer, whereby a pressure-sensitive adhesive layer can be provided on a substrate constituting a laminate. When the present pressure-sensitive adhesive composition contains a vinyl polymer (A) and an acrylic adhesive polymer syrup (C), the present pressure-sensitive adhesive composition is coated on one side or both sides of various substrates, followed by UV, etc. The base material which comprises a laminated body can be equipped with an adhesive layer by polymerizing an acrylic adhesive polymer syrup (C) by irradiating the active energy ray etc. of this. In addition, separately, after obtaining a pressure-sensitive adhesive layer formed from the present pressure-sensitive adhesive composition, the pressure-sensitive adhesive layer may be transferred to one side or both sides of various substrates.

  The pressure-sensitive adhesive layer having a film thickness in the above range may be obtained, for example, by applying a pressure-sensitive adhesive composition having a thickness such that the film thickness is in the above range onto various substrates. It may be obtained by laminating several agent layers.

  The pressure-sensitive adhesive layer included in the laminate has a composition derived from the pressure-sensitive adhesive composition, a first Tg of the entire pressure-sensitive adhesive layer, a second Tg calculated from the composition of the surface layer portion of the pressure-sensitive adhesive layer, and these temperatures. A difference can be provided. More preferably, the peel strength described above can be provided.

  The laminate may have one or more laminate units, and additionally, a separate glass layer via the pressure-sensitive adhesive layer with respect to the transparent resin layer and / or the glass layer of such laminate units. It is also possible to provide a transparent resin layer and / or a layer made of another material. For example, a laminate including a plurality of lamination units can be obtained by laminating the lamination units via the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition. Also, for example, a single layer of a glass layer or a transparent resin layer can be provided via a pressure-sensitive adhesive layer with respect to the lamination unit. That is, a laminated body provided with a glass layer, a transparent resin layer, and a glass layer in order can be obtained by bonding a glass plate together via the adhesive layer on the surface of the transparent resin layer of one lamination | stacking unit.

  The method for producing such a laminate is not particularly limited, and a known method for producing a laminate can be applied. For example, after a transparent resin plate is bonded to one side of a pressure-sensitive adhesive layer (for example, the form of a pressure-sensitive adhesive film can be taken) obtained from the pressure-sensitive adhesive composition, and a glass plate is bonded to the other side. A laminated body (laminated unit) can be obtained by performing the pressure bonding process.

  The glass plate constituting the glass layer of the present laminate is not particularly limited as long as it has transparency and transmits visible light. Although the material which comprises the glass layer in this laminated body is not specifically limited, For example, Soda-lime glass, soda-lime silica glass, aluminosilicate glass, borosilicate glass, a well-known glass, such as phosphate glass, It can be mentioned.

  The thickness of the glass layer is, for example, 30 μm or more and 5000 μm or less. If it is less than 30 μm, it may be broken when it is formed into a laminate, and if it exceeds 5000 μm, the weight becomes too heavy and it becomes difficult to handle.

  The transparent resin board which comprises the transparent resin layer of this laminated body has transparency, and if visible light is transmitted, it will not be specifically limited. Although the material which comprises the transparent resin layer in this laminated body is not specifically limited, For example, polyvinylidene chloride, polyvinyl butyral, a polycarbonate, ethylene-vinyl acetate copolymer resin, polyethylene terephthalate, polymethyl methacrylate, thermoplasticity A fluorine resin etc. are mentioned. Among these, polycarbonate is preferably used because of its good transparency and excellent toughness.

  The thickness of the transparent resin layer is, for example, 100 μm or more and 5000 μm or less. If the thickness is less than 100 μm, the reinforcing property may not be sufficient and breakage may occur. If the thickness exceeds 5000 μm, the transparency may be reduced.

  The pressure-sensitive adhesive layer disclosed herein exhibits high adhesion to both the resin and the glass, and can relieve the stress resulting from the difference in the thermal expansion coefficient of each material, and therefore does not cause defects. It has excellent durability. For this reason, the above-mentioned laminate provided with the present pressure-sensitive adhesive composition can be suitably used for various applications such as a sound insulation wall, a light transmission panel for traffic routes, a protective body of a display device or a housing surface of a portable terminal.

  In addition to the above, from the viewpoint of weight reduction of the glass plate and prevention of scattering when broken, the above-mentioned laminates are various, such as automatic doors, simple roofs such as terraces or carports, sunrooms, daylighting windows, daylighting materials, etc. Can be applied to

[Durability of Laminate]
The pressure-sensitive adhesive layer has a relatively high Tg in its surface layer portion, and thus has good adhesion, but has a relatively low Tg in the vicinity of its center, so that different types of substrates (for example, glass plate and PC plate) Even after pasting together, it is possible to follow the expansion and contraction of these substrates. For this reason, this laminated body can acquire favorable durability (stress relaxation with respect to the stress which arises from the difference in the thermal expansion coefficient of each base material).

  For example, the durability of a laminate obtained by bonding a glass plate and a PC plate via the pressure-sensitive adhesive layer can be evaluated by the following method. That is, a glass plate is attached to one side of a pressure-sensitive adhesive film sample using the pressure-sensitive adhesive composition, and a laminate is prepared by attaching a PC plate to the other side. The stack is then subjected to 20 cycles at 90 ° C for 500 hours, 60 ° C / 90% RH for 500 hours, or -20 ° C / 80 ° C for 20 cycles (30 minutes for each temperature hold time). The appearance after application is observed, and the distance after peeling of the pressure-sensitive adhesive sheet is appropriately measured. For example, the presence or absence of appearance change (peeling of an adhesive sheet) and the distance which peeled are evaluated on the basis of 1 mm.

  The present pressure-sensitive adhesive composition further comprises, as required, a tackifier, a vinyl polymer (A) as a tackifier, an acrylic tacky polymer (B) or an acrylic tacky polymer syrup (C). The composition may also contain additives such as an agent, a plasticizer, an antioxidant, an ultraviolet absorber, an antiaging agent, a flame retardant, an antifungal agent, a silane coupling agent, a filler, and a colorant.

  Tackifiers include rosin esters such as rosin ester, gum rosin, tall oil rosin, hydrogenated rosin ester, maleated rosin, disproportionated rosin ester, etc .; mainly terpene phenol resin, α-pinene, β-pinene, limonene etc. Terpene resins to be used; (hydrogenated) petroleum resins; coumarone-indene resins; hydrogenated aromatic copolymers; styrene resins; phenolic resins; xylene resins; (meth) acrylic polymers and the like.

  As the plasticizer, phthalic acid esters such as di n-butyl phthalate, di n-octyl phthalate, bis (2-ethylhexyl) phthalate, di n-decyl phthalate, diisodecyl phthalate and the like; bis (2-ethylhexyl) adipate, di n -Adipates such as octyl adipate; Sebacates such as bis (2-ethylhexyl) sebacate, di n-butyl sebacate; Azelaic esters such as bis (2-ethylhexyl) azelate; Paraffins such as chlorinated paraffin Glycols such as polypropylene glycol; epoxy-modified vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; phosphoric esters such as trioctyl phosphate and triphenyl phosphate; phosphorous esters such as triphenyl phosphite Ester oligomers such as esters of adipic acid and 1,3-butylene glycol; low molecular weight polymers such as low molecular weight polybutenes, low molecular weight polyisobutylenes, low molecular weight polyisoprenes; oils such as process oils and naphthenic oils Etc.

  As the antioxidant, 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-4-ethylphenol, stearyl-β- (3,5-diphenol) -Tert-Butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4, 4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1-dimethyl-2- [β -(3-tert-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetra Oxaspiro [5.5] undecane, 1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3 ′ -Bis- (4'-hydroxy-3'-tert-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) Phenolic antioxidants such as -S-triazine-2,4,6- (1H, 3H, 5H) trione and tocopherols; dilauryl 3,3'-thiodipro Sulfur-based antioxidants such as onate, dimyristyl 3,3'-thiodipropionate, stearyl 3,3'-thiodipropionate; triphenyl phosphite, diphenyl isodecyl phosphite, 4,4'-butylidene-bis (3-methyl-6-tert-butylphenylditridecyl) phosphite, cyclic neopentanetetrayl bis (octadecyl phosphite), tris (nonylphenyl) phosphite, tris (monononylphenyl) phosphite, tris (diethyl) Nonylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) ) -9, 10- Hydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene, tris (2,4-di-tert-butylphenyl) phos Phyto, cyclic neopentanetetrayl bis (2,4-di-tert-butylphenyl) phosphite, cyclic neopentanetetrayl bis (2,6-di-tert-butyl-4-methylphenyl) phosphite, Phosphorus-based antioxidants such as 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite and the like can be mentioned.

  Examples of UV absorbers include salicylic acid UV absorbers such as phenyl salicylate, p-tert-butylphenyl salicylate and p-octylphenyl salicylate; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy- 4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy Benzophenone-based ultraviolet absorbers such as -5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2) 2 -Hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert) -Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-) Hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- [2'-hydroxy-3'-(3 "] , 4 ′ ′, 5 ′ ′, 6 ′ ′-tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole, 2,2-methylenebis [4 (1,1,3,3-Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2′-hydroxy-5′-methacryloxyphenyl) -2H-benzotriazole, Benzotriazole-based UV absorbers such as 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol]; 2-ethylhexyl- Cyanoacrylate-based ultraviolet light absorbers such as 2-cyano-3,3'-diphenylacrylate, ethyl-2-cyano-3,3'-diphenylacrylate, etc .; nickel bis (octylphenyl) sulfide, [2,2'-thiobis ( 4-tert-Octylphenolate)]-n-butylaminenickel, nickel complex-3,5-di-t Nickel-based ultraviolet light stabilizers such as ert-butyl-4-hydroxybenzyl-phosphate monoethylate, nickel-dibutyldithiocarbamate and the like can be mentioned.

  As an antiaging agent, poly (2,2,4-trimethyl-1,2-dihydroquinoline), 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, 1- (N-phenylamino) ) -Naphthalene, styrenated diphenylamine, dialkyl diphenylamine, N, N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N, N'-di-2-naphthyl-p- Phenylenediamine, 2,6-di-tert-butyl-4-methylphenol, mono (α-methylbenzyl) phenol, di (α-methylbenzyl) phenol, tri (α-methylbenzyl) phenol, 2,2′- Methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-) ert-butylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol), 1,1-bis (4) -Hydroxyphenyl) cyclohexane, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, Examples thereof include nickel dibutyldithiocarbamate, tris (nonylphenyl) phosphite, dilauryl thiodipropionate, and distearyl thiodipropionate.

  As a flame retardant, tetrabromobisphenol A, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, hexabromobenzene, tris (2,3-dibromopropyl) isocyanurate, 2,2-bis Halogen-based flame retardants such as (4-hydroxyethoxy-3,5-dibromophenyl) propane, decabromodiphenyl oxide, halogen-containing polyphosphate, etc .; ammonium phosphate, tricresyl phosphate, triethyl phosphate, tris (β-chloroethyl) Phosphorus-based flame retardants such as phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, acid phosphate ester, nitrogen-containing phosphorus compounds; red phosphorus, tin oxide, ann trioxide Inorganic flame retardants such as mon, zirconium hydroxide, barium metaborate, aluminum hydroxide and magnesium hydroxide; poly (dimethoxysiloxane), poly (diethoxysiloxane), poly (diphenoxysiloxane), poly (methoxyphenoxysiloxane) And siloxane based flame retardants such as methyl silicate, ethyl silicate and phenyl silicate.

  The fungicides include benzimidazole, benzothiazole, trihaloallyl, triazole, organic nitrogen sulfur compounds and the like.

  As a silane coupling agent, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxy Propyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-chloropropylmethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β Examples include (aminoethyl) -γ-aminopropyltrimethoxysilane and the like.

  Examples of the filler include inorganic powder fillers such as calcium carbonate, titanium oxide, mica and talc; and fibrous fillers such as glass fibers and fibers for organic reinforcement.

  In addition, the present pressure-sensitive adhesive composition is not particularly limited in its form as long as it contains a vinyl polymer (A) and an acrylic adhesive polymer (B) or an acrylic adhesive polymer syrup (C). Absent. For example, when the present pressure-sensitive adhesive composition contains a vinyl polymer (A) and an acrylic adhesive polymer (B), it is used as a form of a solvent-type pressure-sensitive adhesive composition dissolved in an organic solvent such as ethyl acetate. It may also be used in the form of an emulsion-type pressure-sensitive adhesive composition in which an acrylic adhesive polymer and a tackifier are dispersed in an aqueous medium. In the case of a solution-type pressure-sensitive adhesive composition and an emulsion-type pressure-sensitive adhesive composition, a medium such as an organic solvent or water used is usually 20 to 80 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive composition.

  When using as an emulsion type adhesive, a stabilizer can be mix | blended. As this stabilizer, for vinyl chloride such as cadmium stearate, zinc stearate, barium stearate, calcium stearate, dibutyltin dilaurate lead, tris (nonylphenyl) phosphite, triphenyl phosphite, diphenyl isodecyl phosphite and the like Stabilizer; di-n-octyltin bis (isooctyl thioglycolic acid ester) salt, di-n-octyltin maleate polymer, di-n-octyltin dilaurate, di-n-octyltin maleate Ester salt, di-n-butyltin bismaleate ester salt, di-n-butyltin maleate polymer, di-n-butyltin bisoctylthio glycol ester salt, di-n-butyltin β-mercaptopropionate polymer, di-n-butyltin -N-Butyltin dilaure , Di-n-methyltin bis (isooctyl mercaptoacetate) salt, poly (thiobis-n-butyltin sulfide), monooctyltin tris (isooctylthio glycolate), dibutyltin maleate, di-n-butyltin malate ester・ Organotin-based stabilizers such as carboxylates and di-n-butyltin malate ester / mercaptide; tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite, dibasic lead phthalate, silica Lead-based stabilizers such as lead acid, dibasic lead stearate and lead stearate; cadmium soaps, zinc soaps, barium soaps, lead soaps, complex metal soaps, metal soap stabilizers such as calcium stearate Etc.

  Hereinafter, specific examples embodying the disclosure of the present specification will be shown. However, the disclosure of the present specification is not limited to the following specific examples. In the following description, “parts” means parts by mass and “%” means mass%.

  The various analyzes in the present specification were performed by the methods described below.

<Solid content>
About 1 g of a measurement sample was weighed (a), and then the residue after drying for 30 minutes at a ventilated dryer 155 ° C. was measured (b) and calculated according to the following equation. A weighing bottle was used for the measurement. Other operations were in accordance with JIS K 0067-1992 (Method for testing weight loss and residue of chemical products).
Solid content (%) = (b / a) x 100

<Molecular weight measurement>
The molecular weight was measured by GPC under the following conditions.
GPC: Tosoh (HLC-8120)
Column: Tosoh (TSKgel-SuperMP-M x 4)
Sample concentration: 0.1%
Flow rate: 0.6 ml / min Eluent: tetrahydrofuran Column temperature: 40 ° C
Detector: Differential Refractometer (RI)
Reference material: polystyrene

<Glass transition point (Tg)>
The Tg of the vinyl polymer (A), the acrylic adhesive polymer (B) and the pressure-sensitive adhesive composition was measured by DSC under the following conditions.
DSC: TA Instrument (Q-100)
Temperature rising temperature: 10 ° C / minute Measuring atmosphere: nitrogen

<Polymer composition>
The polymer composition was calculated from the monomer charge and the monomer consumption by GC measurement.
GC: from Agilent Technologies (7820A GC System)
Detector: FID
Column: 100% dimethyl siloxane (CP-Sil 5CB) Length 30 m, inside diameter 0.32 mm
Calculation method: Internal standard method

1. Synthesis of Vinyl Polymer Synthesis Example 1 (Synthesis of Polymer A-1)
Methyl methacrylate (hereinafter referred to as "MMA") (45 parts by mass), styrene (hereinafter referred to as "St") (5.3 parts by mass), butyl acetate (257 parts by mass) in a 1-liter four-necked flask Part), dimethyl 2,2'-azobis (2-methyl propionate) (the Wako Pure Chemical Industries, Ltd. make, trade name "V-601") (2.7 mass parts) it prepares the mixed liquid which consists of this mixture The solution was sufficiently degassed by bubbling nitrogen gas, and the internal temperature of the mixture was raised to 90.degree. Separately, a mixture consisting of MMA (180 parts by mass), St (19 parts by mass), V-601 (24 parts by mass), and butyl acetate (90 parts by mass) is dropped from the dropping funnel into the flask over 5 hours. The polymerization was carried out by After completion of the dropwise addition, the polymerization solution was added dropwise to hexane (6000 parts by mass) to isolate the vinyl polymer in the polymerization solution to obtain a polymer A-1. The polymer composition of the obtained polymer A-1 was calculated from the charged amount and the monomer consumption by GC measurement, and was composed of 90% by mass of MMA and 10% by mass of St, and was Mw 5600, Mn 3300, Mw / Mn 1.70 The The Tg was 80.degree. Table 1 shows the composition and analysis results of the polymer A-1.

Synthesis Example 2 (Synthesis of Polymer A-2)
A mixed solution of butyl acetate (200 parts by mass) and V-601 (0.9 parts by mass) is charged into a 1-liter four-necked flask, and the mixture is sufficiently degassed by bubbling nitrogen gas. And the internal temperature of the mixture was raised to 90.degree. Separately, a mixture consisting of MMA (165 parts by mass), isobornyl methacrylate (hereinafter referred to as "IBXMA") (44 parts by mass), V-601 (17 parts by mass), and butyl acetate (90 parts by mass) The polymerization was carried out by dropping it into the flask over 5 hours. After completion of the dropwise addition, the polymerization solution is added dropwise to a mixed solution of methanol (4800 parts by mass) and distilled water (1200 parts by mass) to isolate the vinyl polymer in the polymerization solution to obtain a polymer A-2 The Table 1 shows the composition and analysis results of the polymer A-2.

Synthesis Example 3 (Synthesis of Polymer A-3)
A mixed solution consisting of MMA (50 parts by mass), butyl acetate (227 parts by mass) and V-601 (12 parts by mass) is charged into a 1-liter four-necked flask, and this mixed solution is bubbled with nitrogen gas. Degassed sufficiently, and the internal temperature of the mixture was raised to 90.degree. Separately, polymerization was performed by dropping a mixed solution consisting of MMA (200 parts by mass), V-601 (46 parts by mass) and butyl acetate (90 parts by mass) from the dropping funnel into the flask over 5 hours. After completion of the dropwise addition, the polymerization solution was added dropwise to hexane (6000 parts by mass) to isolate the vinyl polymer in the polymerization solution, whereby a polymer A-3 was obtained. The composition and the analysis result of the polymer A-3 are shown in Table 1.

Synthesis Example 4 (Synthesis of Polymer A-4)
A mixed solution of butyl acetate (200 parts by mass) and V-601 (6.2 parts by mass) is charged into a 1-liter four-neck flask, and the mixture is sufficiently degassed by bubbling nitrogen gas. The internal temperature of the mixture was raised to 90.degree. Separately, a mixture consisting of MMA (114 parts by mass), IBXMA (140 parts by mass), V-601 (110 parts by mass), and butyl acetate (90 parts by mass) is dropped from the dropping funnel into the flask over 5 hours. The polymerization was carried out by After completion of the dropwise addition, the polymerization solution is added dropwise to a mixed solution of methanol (4800 parts by mass) and distilled water (1200 parts by mass) to isolate the vinyl polymer in the polymerization solution to obtain a polymer A-4. The Table 1 shows the composition and analysis results of the polymer A-4.

2. Synthesis Example 5 of Acrylic Adhesive Polymer (Synthesis of Polymer B-1)
Methoxyethyl acrylate (hereinafter referred to as "MEA") (500 parts by mass), 2-hydroxyethyl acrylate (hereinafter referred to as "HEA") (27 parts by mass), acetic acid in a 3-liter four-necked flask having an inner volume of Ethyl (980 parts by mass) is charged, the mixture is sufficiently degassed by bubbling nitrogen gas, the internal temperature of the mixture is raised to 75 ° C., and azobisvaleronitrile (hereinafter referred to as "V-65") (0.25 parts by mass) was charged and polymerized for 5 hours. Ethyl acetate was added to a solid concentration of 30% to obtain an ethyl acetate solution of polymer B-1. The obtained polymer was composed of 95% by mass of MEA and 5% by mass of HEA, and had Mw of 520000, Mn of 116000 and Mw / Mn of 4.48. Tg was -31 degreeC.

Synthesis Example 6 (Synthesis of Polymer B-2)
MEA (413 parts by mass), HEA (27 parts by mass), butyl acrylate (hereinafter referred to as "BA") (90 parts by mass), ethyl acetate (980 parts by mass) in a 3-liter four-necked flask The mixture was sufficiently degassed by bubbling nitrogen gas, the internal temperature of the mixture was raised to 75 ° C., V-65 (0.25 parts by mass) was charged, and polymerization was carried out for 5 hours. Ethyl acetate was added to a solid concentration of 30% to obtain an ethyl acetate solution of polymer B-2. The composition and analysis results of the polymer B-2 are shown in Table 2.

3. Preparation of Acrylic Syrup Synthesis Example 7 (Preparation of Syrup C-1)
The ethyl acetate solution of the polymer B-1 was dried under reduced pressure at 60 ° C. for 2 days to obtain a polymer solid content. MEA (66.5 mass parts) and HEA (3.5 mass parts) were added to this polymer solid content (30 weight parts), and syrup C-1 was obtained by stirring until it became uniform. The monomer component which comprises syrup C-1 was MEA95 mass% and HEA5 mass%. The composition of syrup C-1 is shown in Table 3.

Synthesis Example 8 (Preparation of Syrup C-2)
The ethyl acetate solution of the polymer B-2 was dried under reduced pressure at 60 ° C. for 2 days to obtain a polymer solid content. Add MEA (54.6 parts by mass), HEA (3.5 parts by mass), and BA (11.9 parts by mass) to this polymer solid content (30 parts by mass) and stir until uniform. Syrup C-2 was obtained. The composition of syrup C-2 is shown in Table 3.

4. Production and evaluation of adhesive composition Example 1
Polymer A-1 (4 parts by mass) obtained in the above Synthesis Example 1, Syrup C-1 (100 parts by mass) obtained in Synthesis Example 7, Takenate D-110N as a crosslinking agent (manufactured by Mitsui Chemicals, Inc., solid content Solid content (0.4 parts by mass) obtained by drying a concentration of 75%) (0.53 parts by mass) and Irgacure 184 (manufactured by BASF) as a photoinitiator mixed with 0.2 parts by mass of an adhesive The composition was obtained.

The pressure-sensitive adhesive composition was applied to a 50 μm thick polyethylene terephthalate (hereinafter, “PET”) separator to a thickness of 100 μm and 150 μm. A 75 μm-thick PET separator was laminated on the coating film, and irradiated with ultraviolet light with an illuminance of 12.5 mW / cm ² for 2 minutes to polymerize the monomers in the acrylic syrup. Furthermore, the adhesive film sample with a double-sided separator was obtained by leaving still at 40 degreeC for 5 days, and aging (aging).

In addition, a pressure-sensitive adhesive composition was applied on the separator to a thickness of 300 μm, and a pressure-sensitive adhesive film sample was obtained by the same operation as described above except that ultraviolet light with an illuminance of 12.5 mW / cm ² was irradiated for 4 minutes.

Examples 2 to 4
About these examples, based on the composition shown in Table 4, it operated similarly to Example 1 and obtained the adhesion film sample.

Example 5
A polymer (A-2) solution having a solid content concentration of 30% by mass, in which a polymer A-2 (8 parts by mass) is dissolved in ethyl acetate, is mixed with a solution of a polymer B-2, A solution having a solid content of 30% by mass containing 8 parts by mass) and polymer B-2 (100 parts by mass) was prepared. Here, Takenate D-110N (0.53 mass parts) (0.4 mass parts as solid content) was mixed as a crosslinking agent, and the adhesive composition was obtained.

The pressure-sensitive adhesive composition was applied onto a separator made of polyethylene terephthalate (hereinafter, “PET”) having a thickness of 75 μm so as to have a thickness after drying of 100 μm, 150 μm and 300 μm. The ethyl acetate was removed by drying the pressure-sensitive adhesive composition under the following drying conditions. A 50 μm-thick PET separator having a different peel strength was attached to the above-mentioned separator, and allowed to stand at 40 ° C. for 5 days for aging (aging) to obtain an adhesive film sample with a double-sided separator. Foaming was not observed under any of the drying conditions.
«Drying conditions»
100 μm: 60 ° C. × 2 minutes + 80 ° C. × 4 minutes 150 μm: 60 ° C. × 3 minutes + 80 ° C. × 4 minutes 300 μm: 60 ° C. × 6 minutes + 80 ° C. × 4 minutes

Comparative Examples 1 to 3
About these comparative examples, based on the composition shown in Table 5, it carried out similarly to Example 1, and obtained the adhesion film sample.

Comparative Examples 4 and 5
For Comparative Example 4, a pressure-sensitive adhesive film sample was obtained by the same operation as in Example 1 except that the pressure-sensitive adhesive composition was applied to a thickness of 50 μm on the separator. For Comparative Example 5, an adhesive film was applied in the same manner as Example 5, except that the pressure-sensitive adhesive composition was applied on the separator so that the thickness after drying was 50 μm, and the drying conditions were 80 ° C. and 4 minutes. A sample was obtained.

(Evaluation etc.)
About the obtained adhesive film sample, various measurement and evaluation were performed by the method shown next. The obtained results are shown in Tables 4 to 5.

<Gel fraction>
0.2 g of the adhesive was taken from the adhesive film sample, and the initial weight of the adhesive was weighed. The adhesive is immersed in 50 g of ethyl acetate and allowed to stand at room temperature for 16 hours. Thereafter, the resultant was filtered through a 200 mesh wire mesh, and the residue remaining on the mesh was dried at 80 ° C. for 3 hours and weighed. The gel fraction was calculated from the initial weight and the remaining weight.

<Haze value>
The release film was peeled off from the adhesive film (50 μm) sample, transferred to a glass plate (1 mm thick), and the other release film was peeled off. After standing for 1 day under conditions of 23 ° C. and 50% RH, the haze value was measured using a haze meter “Haze meter NDH 2000” (type name) manufactured by Nippon Denshoku Co., Ltd.

<Tg of surface layer of pressure-sensitive adhesive layer>
From the peak area ratio of O1s and C1s by X-ray photoelectron spectroscopy (XPS) measurement of adhesive film sample, relative to the total amount of vinyl polymer (A) and acrylic syrup (B ') after polymerization in the surface layer part of adhesive layer The mass fractions (w _A and w _B ) of the vinyl polymer (A) and the acrylic syrup (B ') after polymerization were calculated, and the Tg of the surface layer was calculated based on the formula of FOX.
The XPS measurement was performed under the following conditions.
Device: ULVAC-PHI PHI5000 VersaProbe
X-ray: Al-Kα (1486.6 eV)
X-ray incidence angle to the sample: 0 ° (angle to the normal of the sample measurement surface)
Photoelectron detection angle: 45 ° (angle to the normal of the sample measurement surface)

ここで、
（Ｏ／Ｃ）_Ａ+B：粘着剤組成物を重合してから得られた粘着剤層のＸＰＳ測定から求められるＯ１ｓとＣ１ｓのピーク面積比
Ｗ_Ａ：ビニル重合体（Ａ）と、アクリル系粘着性ポリマー（Ｂ）またはアクリル系粘着性ポリマーシロップ（Ｃ）と、の総量に対するビニル重合体（Ａ）の質量分率
Ｍ_ｗ−Ａ：ビニル重合体（Ａ）の全構成単量体単位の加重平均分子量
Ｍ_ｗ−Ｂ：アクリル系粘着性ポリマー（Ｂ）またはアクリル系粘着性ポリマーシロップ（Ｃ）の全構成単量体単位の加重平均分子量
Ｎ_Ｏ−Ａ：ビニル重合体（Ａ）を構成する全構成単量体の平均単量体構造式中に含まれる酸素原子数
Ｎ_Ｏ−Ｂ：アクリル系粘着性ポリマー（Ｂ）またはアクリル系粘着性ポリマーシロップ（Ｃ）を構成する全構成単量体の平均単量体構造式中に含まれる酸素原子数
Ｎ_Ｃ−Ａ：ビニル重合体（Ａ）を構成する全構成単量体の平均単量体構造式中に含まれる炭素原子数
Ｎ_Ｃ−Ｂ：アクリル系粘着性ポリマー（Ｂ）またはアクリル系粘着性ポリマーシロップ（Ｃ）を構成する全構成単量体の平均単量体構造式中に含まれる炭素原子数 The concrete calculation method of the said mass fraction is described below.
The peak area ratio of O1s to C1s measured by XPS is a pressure-sensitive adhesive layer formed of a pressure-sensitive adhesive composition comprising a vinyl polymer (A) and an acrylic adhesive polymer (B) as shown in the following formula (1) The number of oxygen atoms and the number of carbon atoms present per unit mass of the surface layer portion of the pressure-sensitive adhesive layer formed by polymerizing a pressure-sensitive adhesive composition comprising a vinyl polymer (A) and an acrylic adhesive polymer syrup (C) It is expressed by a ratio.

here,
(O / C) _{A + B} : Peak area ratio of O1s to C1s obtained from XPS measurement of the pressure-sensitive adhesive layer obtained by polymerizing the pressure-sensitive adhesive composition W _A : Vinyl polymer (A) and acrylic Mass fraction of vinyl polymer (A) with respect to the total amount of adhesive polymer (B) or acrylic adhesive polymer syrup (C) _Mw-A : of all constituent monomer units of vinyl polymer (A) Weighted average molecular weight _Mw-B : Weighted average molecular weight NO _-A of all constituent monomer units of acrylic adhesive polymer (B) or acrylic adhesive polymer syrup (C): vinyl polymer (A) The number of oxygen atoms contained in the average monomer structural formula of all constituent monomers to be formed N _O-B : All constituent single amounts constituting the acrylic adhesive polymer (B) or the acrylic adhesive polymer syrup (C) In the average monomer structure of the body Murrell oxygen atom number N _C-A: vinyl polymer the number of carbon atoms contained averaged in the monomer structure of the total constituent monomer constituting the (A) N _C-B: acrylic adhesive polymer (B ) Or the number of carbon atoms contained in the average monomer structural formula of all constituent monomers constituting the acrylic adhesive polymer syrup (C)

ここで、
（Ｏ／Ｃ）_Ａ：ビニル重合体（Ａ）のフィルムのＸＰＳ測定から求められるＯ１ｓとＣ１ｓのピーク面積比

ここで、
（Ｏ／Ｃ）_Ｂ：アクリル系粘着性ポリマー（Ｂ）またはアクリル系粘着性ポリマーシロップ（Ｃ）のフィルムのＸＰＳ測定から求められるＯ１ｓとＣ１ｓのピーク面積比 In addition, the peak area ratio of O1s to C1s determined by XPS measurement of the film of each of the vinyl polymer (A) and the acrylic adhesive polymer (B) of the formed pressure-sensitive adhesive layer is represented by the following formula (2) and It is represented by (3).

here,
(O / C) _A : Peak area ratio of O1s to C1s obtained from XPS measurement of a film of vinyl polymer (A)

here,
(O / C) _B : Peak area ratio of O1s to C1s determined from XPS measurement of a film of acrylic adhesive polymer (B) or acrylic adhesive polymer syrup (C)

さらに、上記で求めたＷ_Ａの値と下記式（５）から、アクリル系粘着性ポリマー（Ｂ）またはアクリル系粘着性ポリマーシロップ（Ｃ）の質量分率（Ｗ_Ｂ）が算出される。

ここで、
Ｗ_Ｂ：ビニル重合体（Ａ）及びアクリル系粘着性ポリマー（Ｂ）またはアクリル系粘着性ポリマーシロップ（Ｃ）の総量に対するアクリル系粘着性ポリマー（Ｂ）またはアクリル系粘着性ポリマーシロップ（Ｃ）の質量分率 The following formula (4) is derived from the above formulas (1) to (3), from which the total amount of vinyl polymer (A) and acrylic adhesive polymer (B) or acrylic adhesive polymer syrup (C) is derived. mass fraction of the vinyl polymer _{(a) (W} a) is calculated.

Furthermore, the mass fraction (W _B ) of the acrylic adhesive polymer (B) or the acrylic adhesive polymer syrup (C) is calculated from the value of W _A determined as described above and the following formula (5).

here,
W _B : Acrylic adhesive polymer (B) or acrylic adhesive polymer syrup (C) based on the total amount of vinyl polymer (A) and acrylic adhesive polymer (B) or acrylic adhesive polymer syrup (C) Mass fraction

Each element in the above-mentioned formula (4) about Example 1 is shown below.
(O / C) _{A + B} : 0.320 (measured value)
(O / C) _A : 0.308 (measured value)
(O / C) _B : 0.474 (measured value)
N _C-A : From the number of carbon atoms in one MMA molecule (5), the number of carbon atoms in one St1 molecule (8) and the composition ratio, 5 × 90 (%) + 8 × 10 (%) = 5.3
NC _-B : From the number of carbon atoms in one MEA molecule (6), the number of carbon atoms in one HEA molecule (5) and the composition ratio, 6 x 94 (%) + 5 x 6 (%) = 5.9
_Mw-A : MMA molecular weight (100), St molecular weight (104) and composition ratio, 100 x 90 (%) + 104 x 10 (%) = 100
M _w-B : From the molecular weight of MEA (130), the molecular weight of HEA (116) and the composition ratio, 130 × 94 (%) + 116 × 6 (%) = 129
By substituting these values into the equation (4), W _A = 0.92 was obtained, and from the equation (5), W _B = 0.08 was obtained.

Next, according to the formula of FOX represented by the following formula (6), the Tg of the surface layer portion was calculated from the surface composition obtained for measurement, and a value of 67.5 ° C. was obtained.
1 / [Tg of the surface layer portion] _{(K) = W A / Tg} A + W B / Tg B (6)
here,
Tg _A : Tg (80 ° C.) of vinyl polymer (A)
Tg _B : Tg (−31 ° C.) of acrylic adhesive polymer syrup (C) after polymerization

<Peeling strength to polycarbonate (PC) and glass>
The pressure-sensitive adhesive film sample was transferred to a PET film (100 μm) subjected to easy adhesion treatment, and then cut into 25 mm wide strips to obtain a pressure-sensitive adhesive sheet for evaluation. The adherend is a PC board (Mitsubishi Gas Chemical Co., Ltd., Iupilon NF 2000, 1.5 mm thick) or a glass board (Asahi Glass Co., Ltd., Fabritech FL11A, 1 mm thick), and the adhesive sheet for the above evaluation is laminated. After pressure bonding using pressure degassing apparatus TBR-200 (manufactured by Chiyoda Denki Co., Ltd.) under the conditions of 0.5 MPa and 50 ° C. for 20 minutes, a tensile tester with a thermostat bath strograph R type (manufactured by Toyo Seiki Co., Ltd.) The temperature is 23 ° C. and 85 ° C., the peeling speed is 300 mm / min. The 180-degree peel strength of the pressure-sensitive adhesive sheet was measured in accordance with JIS Z-0237 "pressure-sensitive adhesive tape / pressure-sensitive adhesive sheet test method" under the conditions described in Table 1 as adhesion strength.

<Durability of Laminate>
A laminated body in which glass is pasted to one side of a 5 cm × 6 cm adhesive film sample and a PC board is pasted to the other side is prepared, and pressure bonding treatment of 50 ° C., 0.5 MPa for 20 minutes is performed on the layered body. went. Thereafter, the laminate is loaded for 20 hours at 90 ° C., 500 hours at 60 ° C./90% RH, or 20 cycles of thermal cycle of −20 ° C./80° C. (holding time for each temperature is 30 minutes). The subsequent appearance (peeling from the end) was visually confirmed and evaluated according to the following criteria.
○: No peeling Δ: The maximum distance peeled off from the end of the adhesive sheet is 1 mm or less ×: The maximum distance peeled from the end of the adhesive sheet exceeds 1 mm

  As shown in Table 4, in each of Examples 1 to 5 using the pressure-sensitive adhesive composition disclosed herein, the Tg of the surface layer portion of the pressure-sensitive adhesive layer is 60 ° C. than the Tg of the entire pressure-sensitive adhesive layer. It was high above and showed good peel strength under each condition. Among them, the Tg of the surface layer portion of the pressure-sensitive adhesive layer is 90 ° C. or more higher than the Tg of the entire pressure-sensitive adhesive layer, and the Tg of the surface layer portion of the pressure-sensitive adhesive layer is 60 ° C. or more under high temperature conditions (85 ° C.) The results show good adhesion.

  In addition, as shown in Table 4, the laminate having a pressure-sensitive adhesive layer with a thickness of 100 μm or more (glass / this pressure-sensitive adhesive layer / PC) resulted in having good durability. That is, the results show that the stress generated by the difference between the thermal expansion coefficient of the glass and that of the PC can be suitably relieved under high temperature conditions, high humidity conditions, cold cycle conditions, and the like.

In contrast, as shown in Table 5, in Comparative Examples 1 and 2 in which the pressure-sensitive adhesive composition containing no vinyl polymer (A) was used, the distribution of Tg in the pressure-sensitive adhesive layer was not observed, and each condition In particular, the peel strength under high temperature conditions is lowered, and the durability of the laminate is also insufficient. Moreover, in Comparative Example 3, the vinyl polymer (A) was not sufficiently segregated in the formed pressure-sensitive adhesive layer, so the peel strength was low and the durability of the laminate was not sufficient. Furthermore, in Comparative Examples 4 and 5, although having the same composition as Examples 1 and 5, the film thickness of the pressure-sensitive adhesive layer used in the laminate was a relatively thin film of 50 μm, so the thermal expansion of glass and PC The stress caused by the difference in the coefficients could not be suitably alleviated, and good durability could not be exhibited.

Claims (7)

A laminate comprising a lamination unit having a transparent resin layer and a glass layer disposed via an adhesive layer,
The pressure-sensitive adhesive layer contains a vinyl polymer (A) and an acrylic adhesive polymer (B), and has a thickness of 100 μm to 5 mm,
The vinyl polymer (A) has a glass transition temperature (Tg) of 30 ° C. or more and 200 ° C. or less, a number average molecular weight of 500 to 10,000, and 100 parts by mass of the acrylic adhesive polymer (B) To 0.5 parts by mass to 60 parts by mass,
The second Tg, which is the glass transition temperature calculated from the surface layer portion obtained by X-ray photoelectron spectroscopy analysis of the pressure-sensitive adhesive layer, is 30 ° C. or more than the first Tg, which is the glass transition temperature of the entire pressure-sensitive adhesive layer High, laminated.   The laminated body of Claim 1 whose said 1st Tg is -80 degreeC or more and 10 degrees C or less.   The laminated body of Claim 1 or 2 whose Tg of the said vinyl polymer (A) is 60 degreeC or more and 200 degrees C or less.   The laminate according to any one of claims 1 to 3, wherein the pressure-sensitive adhesive layer further comprises a crosslinking agent.   The adhesive sheet comprising a 100 μm thick polyethylene terephthalate film substrate with a 150 μm thick adhesive layer, has a peel strength to a polycarbonate plate at a peel rate of 300 mm / min at 85 ° C. of 8.0 N / 25 mm or more. The laminate according to any one of claims 1 to 4, wherein the peel strength to a glass plate at a peel rate of 300 mm / min at 85 ° C is 6.0 N / 25 mm or more.   The laminate according to any one of claims 1 to 5, wherein the acrylic adhesive polymer (B) is formed by polymerizing an acrylic adhesive polymer syrup (C). A method of manufacturing a laminate,
The laminate has a lamination unit comprising a transparent resin layer and a glass layer via an adhesive layer,
The pressure-sensitive adhesive composition described below between the transparent resin layer and the glass layer;
The vinyl polymer (A), the acrylic adhesive polymer syrup (C), and the polymerization initiator are contained, and the vinyl polymer (A) has a glass transition temperature (Tg) of 30 ° C. or more and 200 ° C. Or less, having a number average molecular weight of 500 to 10,000, and 0.5 to 60 parts by mass with respect to the acrylic adhesive polymer syrup (C),
Forming the pressure-sensitive adhesive layer by polymerizing the acrylic pressure-sensitive adhesive polymer syrup (C) in to form the laminated unit,
A manufacturing method.