Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
  • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
  • H10F19/85—Protective back sheets
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
  • B32B2307/206—Insulating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/30—Properties of the layers or laminate having particular thermal properties
  • B32B2307/306—Resistant to heat
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/712—Weather resistant
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/718—Weight, e.g. weight per square meter
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/724—Permeability to gases, adsorption
  • B32B2307/7242—Non-permeable
  • B32B2307/7246—Water vapor barrier
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2405/00—Adhesive articles, e.g. adhesive tapes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2312/00—Crosslinking
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy

Definitions

• the present invention relates to a resin composition for sheet adhesion used for adhesion of plastic films, metal foils, etc., and a laminate, a solar cell protective sheet and a solar cell module using the same.
• a metal foil such as a steel plate, a metal plate or a metal vapor deposition film and a plastic film such as a polypropylene resin, a polyvinyl chloride resin, a polyester resin, a fluorine resin, or a polypropenoic acid ester resin are laminated and laminated ( Laminated) has been used.
• a resin composition for adhering a metal foil, a metal plate or a metal vapor-deposited film, and a plastic film a resin composition for adhering a sheet of polyepoxy resin, or a polyurethane resin
• a resin composition for sheet adhesion is known.
• a simple solar battery module used for a solar battery has a configuration in which a filler and a glass plate are sequentially laminated on both surfaces of a solar battery cell which is a solar battery element. Since a glass plate is excellent in transparency, weather resistance, and scratch resistance, it is still generally used as a sealing sheet on the solar light receiving surface side.
• solar cell protective sheets other than glass plates hereinafter referred to as “protective sheets”.
• the protective sheet As the protective sheet, a two-component cross-linkable adhesive using a main resin and a cross-linking agent is generally used.
• the two-component cross-linkable adhesive is applied to a film and dried. It is manufactured by laminating films or metal foils, curing the laminated body at about 20 to 60 ° C. for several days, and terminating the curing reaction accompanying crosslinking. Therefore, the two-component cross-linking adhesive used for the protective sheet has sufficient initial adhesion to the film during lamination and sufficient adhesive strength to the film after curing, heat resistance, weather resistance, water vapor permeability, hydrolysis resistance It is important to have excellent properties.
• Materials used for the protective sheet include polyester resin film, polyethylene resin film, polypropylene resin film, polyvinyl chloride resin film, polycarbonate resin film, polysulfone resin film, poly (2-methyl) propenoic acid ester
• films in which metal oxides or non-metallic inorganic oxides are vapor-deposited on these, and metal foils such as aluminum foil and copper foil are used.
• PET polyethylene terephthalate
• PEN polyethylene naphthalate
• a protective sheet is generally used in which a metal foil such as a plastic film or aluminum foil on which a metal inorganic oxide is deposited and a fluororesin film are laminated.
• a solar cell module is manufactured by bonding, for example, glass / solar cell / protective sheet through a sealing material such as ethylene vinyl acetate resin (EVA).
• EVA ethylene vinyl acetate resin
• the protective sheet is required to have heat resistance in order to be crimped at high temperature under vacuum.
• the protective sheet needs to have excellent adhesiveness even after being exposed to the outdoors for a long period of time, and is required to have excellent hydrolysis resistance as well as adhesion after curing.
• a color difference change is very small and the outstanding weather resistance is calculated
• Examples of the configuration of these protective sheets include a laminate of insulating film / bonding agent / water vapor barrier film / bonding agent / weather resistant film from the solar cell side.
• Examples of the insulating film include a fluorine-based resin film, a PET-based film, and an EVA-based film.
• Examples of the film having a water vapor barrier property include a silica-deposited PET-based film, an aluminum oxide-deposited PET-based film, and an aluminum foil.
• Examples of the weather resistant film that is the outermost layer include a fluorine resin film, a PET film, and a polyethylene film.
• As the bonding agent a resin composition for sheet adhesion having excellent adhesion to these various substrates is required.
• Patent Document 1 discloses a resin composition for sheet adhesion using a polyester resin and a polyurethane resin in consideration of balance, which can give excellent initial cohesive force and adhesive force.
• Patent Document 2 discloses a resin composition for sheet adhesion using a polyurethane-based resin that is excellent in hot water resistance during retort sterilization in food packaging.
• Patent Document 3 discloses a pressure-sensitive adhesive composition for an optical member used for bonding an optical film such as a polarizing film blended with a polypropenoic ester resin.
• Patent Document 4 discloses a resin composition for sheet bonding used for an optical element blended with a propenoic acid resin.
• Patent Document 5 discloses the use of a sheet-adhesive resin composition using a hydrolysis-resistant polyurethane-based resin in the back protective sheet.
• Patent Document 6 discloses a solar cell back surface protection sheet provided with an adhesion improving layer composed of a resin composition for sheet adhesion using a polyester resin or a polyester polyurethane resin.
• Patent Documents 7 and 8 disclose a back surface protection sheet using a resin composition for sheet adhesion of a polypropenoic acid ester resin.
• JP-A-10-218978 Japanese Patent Laid-Open No. 06-116542 JP 2005-298723 A Patent 4824544 JP 2008-4691 A JP 2007-136911 A JP 2010-263193 A JP 2012-142349 A
• each of them forms a two-component curable adhesive coating film using a crosslinking agent, but the main component is a polyester-based resin.
• the cohesive force of the resin composition for sheet adhesion after the curing reaction accompanying crosslinking may be reduced, and a plurality of films constituting the solar cell protective sheet may be peeled off.
• attachment of the 2 liquid curing type which used together the isocyanate group containing crosslinking agent is formed, all are the isocyanate group excess designs, and isocyanate. Since the curing reaction accompanying the crosslinking of the groups is not completed, the remaining isocyanate groups react with moisture, causing decarboxylation, and foaming may occur during the durability test.
• the glass transition point of the resin is adjusted to try to improve the adhesive strength, but various surface tension, film thickness, and elasticity are different.
• the adhesive strength to the substrate cannot be obtained, and by designing with only a single resin, the application range for various substrates is narrow, and securing the adhesive strength may be difficult.
• the present invention has been made in order to solve such a problem, and the problem is to provide a sheet-adhesive resin composition excellent in adhesiveness and durability after a curing reaction accompanying crosslinking, and the sheet-adhesive resin composition. It is to provide a solar cell protective sheet and a solar cell module to be used.
• the present inventors have found that the above-mentioned goal can be achieved by the following resin composition for bonding a sheet, and have completed the present invention.
• a resin composition for sheet adhesion comprising a main resin and a crosslinking agent (C) for the main resin,
• the main resin is a copolymer (A) and a copolymer (B) containing an active hydrogen group (however, one kind selected from the group consisting of a carboxyl group, an amide group, a carbonyl group and an N-alkoxyalkyl group)
• a resin composition for sheet adhesion containing the above (excluding ⁇ , ⁇ -unsaturated compounds having a functional group) and satisfying the following (1) and (2).
• the copolymer (A) is obtained by copolymerizing an ⁇ , ⁇ -unsaturated compound, and has a glass transition point (Tg) of ⁇ 40 ° C.
• the copolymer (B) is obtained by copolymerizing an ⁇ , ⁇ -unsaturated compound, and has a glass transition point (Tg) of 10 ° C. or higher and lower than 110 ° C.
• the copolymer (B) is composed of an ⁇ , ⁇ -unsaturated compound (m-2) having an active hydrogen group (excluding those that are (m-1)) and other copolymerizable ⁇ , ⁇ -unsaturated compounds.
• the resin composition for sheet bonding according to [1] which is obtained by copolymerizing a saturated compound (m-3) (excluding those which are (m-1) and (m-2)) .
• Copolymer (A) contains 0.01 to 10 parts by weight of ⁇ , ⁇ -unsaturated compound (m-1) in 100 parts by weight of ⁇ , ⁇ -unsaturated compound used for copolymerization,
• Copolymer (B) is ⁇ , ⁇ -unsaturated compound (m-2) (however, (m-1) in 100 parts by weight of ⁇ , ⁇ -unsaturated compound used for copolymerization) Excluded) 0.01-20 parts by weight and other copolymerizable ⁇ , ⁇ -unsaturated compound (m-3) (except for those that are (m-1) and (m-2)) 80-
• the resin composition for sheet bonding according to any one of [2] or [3], which is obtained by copolymerizing 99.99 parts by weight.
• the copolymer (A) is included in a range of 30 to 95 parts by weight in a total of 100 parts by weight of the copolymer (A) and the copolymer (B) [1] to [ 4]
• the copolymer (A) has a weight average molecular weight of 50,000 to 1,000,000, and the copolymer (B) has a weight average molecular weight of 2,000 to 80,000.
• the resin composition for sheet bonding according to any one of [1] to [5].
• the crosslinking agent (C) is a polyisocyanate compound (c-1), a polyfunctional epoxy compound (c-2), a metal chelate compound (c-3), a carbodiimide compound (c-4), and an aziridine compound (C
• the polyisocyanate (c-1) is an aliphatic polyisocyanate (c-1-1) and / or an alicyclic polyisocyanate compound (c-1-2) [8] The resin composition for sheet
• a laminate comprising a layer made of the resin composition for sheet bonding according to any one of [1] to [9], which is laminated on one side or both sides of the substrate (G).
• the resin composition for sheet adhesion of the present invention By using the resin composition for sheet adhesion of the present invention, it is possible to provide a laminated sheet having excellent adhesive strength on various substrates, high durability, and excellent weather resistance. Moreover, since it is a lamination sheet excellent in the adhesiveness and durability after hardening reaction accompanying bridge
• the resin composition for sheet bonding according to the present invention includes a main resin and a cross-linking agent (C) for the main resin, and two types of glass resins having different glass transition points (hereinafter also referred to as “Tg”) are used as the main resin.
• a resin that is, a copolymer (A) and a copolymer (B) are included. Details will be described below.
• the copolymer (A) of the present invention is obtained by copolymerizing an ⁇ , ⁇ -unsaturated compound, adjusting the composition ratio of the ⁇ , ⁇ -unsaturated compound, and having a glass transition point (Tg) of ⁇ 40 ° C. or higher. It is a copolymer which becomes less than 10 degreeC.
• the copolymer (A) comprises (i) the adhesion to the film during lamination, and (ii) the balance between the wettability and the cohesive force in the cured coating film after the curing reaction accompanying the crosslinking of the resin composition for sheet adhesion. Therefore, the glass transition point of the copolymer (A) is preferably adjusted to a range of ⁇ 40 ° C. or more and less than 10 ° C., more preferably ⁇ 30 ° C. or more and less than 0 ° C., ⁇ 20 ° C. or more, ⁇ 5 ° C. Less than is more preferable.
• the cohesive force in the cured coating film of the sheet-adhesive resin composition may be insufficient, and the adhesive force may be reduced. Since the wettability decreases, the adhesion to the film during lamination may decrease. If the Tg of a homopolymer that can be formed from each monomer that is a constituent component of the copolymer (A) is known, the copolymer is based on the Tg of each homopolymer and the constituent ratio of each monomer. The Tg of the polymer (A) can be determined theoretically.
• the value described in literature can be used for Tg of a homopolymer.
• the following documents can be referred to: acrylic rayon catalog of Mitsubishi Rayon (2001 version); catalog of Osaka Organic Chemical Industry (2009 version); funkrill catalog of Hitachi Chemical Co., Ltd. ( 2007 edition); and “POLYMER HANDBOOK” 3rd edition, pages 209-277, John Wiley & Sons, Inc., 1989.
• the glass transition point (° C.) of a homopolymer of the following monomer is as follows.
• the weight average molecular weight of the copolymer (A) is 50,000 to 1,000,000 (upper limit value and lower limit value) in order to ensure the coating suitability of the resin composition for sheet adhesion and the cohesive strength of the cured coating film. (The same applies hereinafter)), preferably 100,000 to 500,000, and more preferably 150,000 to 300,000.
• the weight average molecular weight is less than 50,000, the cohesive force of the cured coating film is insufficient, and cohesive failure may occur and the adhesive force may be reduced.
• the weight average molecular weight exceeds 1,000,000, the copolymer (A) Viscosity is high, and coatability may be deteriorated.
• the weight average molecular weight is in the range of 150,000 to 300,000, it is easy to achieve a balance between the wettability of the cured coating film with respect to the substrate, the cohesive force, and the viscosity, and exhibit stress relaxation properties.
• the molecular weight distribution (weight average molecular weight / number average molecular weight) of the copolymer (A) is preferably in the range of 2 to 8, and more preferably 3 to 6.
• the molecular weight distribution (weight average molecular weight / number average molecular weight) is less than 2, since there are few low molecular weight components, the leveling property at the time of lamination may be reduced, and the initial adhesion to the film may be reduced.
• the weight average molecular weight / number average molecular weight) exceeds 8, the thixotropy becomes too high, and uneven coating or the like may occur during coating, resulting in poor appearance of the coating film.
• the ⁇ , ⁇ -unsaturated compound used in the copolymer (A) is not limited as long as it is a known compound, and among these, a carboxyl group, an amide group, a carbonyl group and an N-alkoxyalkyl group can be used. It is preferable to use an ⁇ , ⁇ -unsaturated compound (m-1) (hereinafter also simply referred to as (m-1)) having one or more functional groups selected from the group consisting of When the below-mentioned crosslinking agent (C) has a functional group capable of chemically reacting with the functional group in (m-1), the functional group in (m-1) can be obtained by using (m-1).
• the functional group contained in the crosslinking agent (C) effectively cause a curing reaction accompanying crosslinking.
• attachment is attained.
• the effect which raises the interaction between resin is large, and the cohesion force of a cured coating film improves remarkably.
• the effects of the functional group contained in (m-1) include not only the curing reaction associated with general crosslinking as described above, but also the functional group contained in (m-1), as well as hydroxyl groups and mercapto.
• the isocyanate group exhibits a resonance structure as represented by the general formula (1).
• the amino group and the amide group are N ⁇ —C +. It is thought that the reaction with active hydrogen is promoted by shifting the equilibrium to ⁇ O.
• 0.01 to 10 parts by weight of ⁇ , ⁇ -unsaturated compound (m-1) is contained in 100 parts by weight of ⁇ , ⁇ -unsaturated compound used for copolymerization of copolymer (A). It is more preferably 1 to 5 parts by weight, and further preferably 0.2 to 2 parts by weight.
• the amount is less than 0.01 part by weight, not only the cohesive force of the cured coating film is improved due to the curing reaction accompanying the crosslinking with the crosslinking agent (C), but also the catalytic effect accompanying the acceleration of the reaction may not be obtained.
• ⁇ -unsaturated compounds (m-1) having one or more functional groups selected from the group consisting of a carboxyl group, an amide group, a carbonyl group and an N-alkoxyalkyl group, ⁇ , ⁇ containing a carboxyl group -As unsaturated compounds,
• (2-methyl) propenoic acid [propenoic acid and 2-methylpropenoic acid are collectively referred to as “(2-methyl) propenoic acid”.
• ⁇ -unsaturated compound containing an amide group For example, (2-methyl) 2-propenamide, 2-methylpropene-2-enoylamide, N, N-dimethyl-2-propenamide, N, N-diethyl-2-propenamide, N- [3- (N ', N'-dimethylamino) propyl] -2-propenamide, N-isopropyl-2-propenamide, N-ethenylacetamide, N-ethenyl- ⁇ -methylthioacetamide, N-ethenylformamide, N-hydroxymethyl -Ethenyls containing aliphatic amide groups such as -2-propenamide;
• Examples of ⁇ , ⁇ -unsaturated compounds containing a carbonyl group include For example, 2- (1,3-dioxobutoxy) ethyl (2-methyl) propenoate, 2- (1,3-dioxobutoxy) propyl (2-methyl) propenoate, 3- (2-methyl) propenoate 3- ( 1,3-dioxobutoxy) propyl, 2- (1,3-dioxobutoxy) butyl (2-methyl) propenoate, 3- (1,3-dioxobutoxy) butyl (2-methyl) propenoate, (2- ⁇ -diketone structure-containing (2-methyl) propenoates such as methyl) propenoate 4- (1,3dioxobutoxy) butyl:
• ketone structure-containing ethenyls such as N- (1,1-dimethyl-3-oxobutyl) -2-propenamide and N- (1,1-dimethyl-3-oxobutyl) -2-methyl-2-propenamide Is mentioned.
• Examples of ⁇ , ⁇ -unsaturated compounds containing N-alkoxyalkyl groups include N-methoxymethyl-2-propenamide, N-ethoxymethyl (2-methyl) propenamide, N- (n-, iso-) Butoxymethyl (2-methyl) propenamide, N-methoxyethyl (2-methyl) propenamide, N-ethoxyethyl (2-methyl) propenamide, N- (n-, iso-) butoxyethyl (2-methyl) And propenamide.
• ⁇ , ⁇ -unsaturated compound (m-1), (2-methyl) propenoic acid from the viewpoint of the completion of the curing reaction accompanying crosslinking with the crosslinking agent (C) and the efficiency of the catalytic effect, 2-methylenesuccinic acid and (2-methyl) 2-propenamide are preferred.
• the copolymerization of an ⁇ , ⁇ -unsaturated compound other than (m-1) used in the copolymer (A) will be described later.
• (M-1) may be a single type or a combination of two or more types.
• the copolymer (B) of the present invention is obtained by copolymerizing an ⁇ , ⁇ -unsaturated compound, adjusting the composition ratio of the ⁇ , ⁇ -unsaturated compound, and having a glass transition point (Tg) of 10 ° C. or higher. It is a copolymer which becomes less than 110 degreeC.
• the Tg of the copolymer (B) is adjusted to a range of 10 ° C. or more and less than 110 ° C. from the adhesiveness to the film at the time of lamination and the balance of cohesive force accompanying the entropy elasticity of the resin composition for sheet adhesion. Is preferably 20 ° C. or higher and lower than 80 ° C., more preferably 25 ° C. or higher and lower than 60 ° C.
• Tg is less than 10 ° C.
• the effect of increasing the cohesive force associated with the elasticity of the resin composition for sheet adhesion is low, the internal cohesive force may be reduced and the adhesive force may be reduced.
• the compatibility with the copolymer (A) is deteriorated, the wettability of the resin composition for sheet adhesion is decreased, and the initial adhesiveness to the film at the time of lamination may be decreased.
• Tg 25 ° C. or more and less than 60 ° C. it is easy to achieve a balance between cohesive force and viscosity, compatibility, and internal cohesive force accompanying entropy elasticity.
• the Tg of the homopolymer that can be formed from each monomer that is a constituent component of the copolymer (B) is known, the Tg of each homopolymer and the constituent ratio of each monomer are the same as above. Based on the above, the Tg of the copolymer (B) can be theoretically determined by the FOX equation.
• the weight average molecular weight of the copolymer (B) is preferably from 2,000 to 80,000, and preferably from 5,000 to 50 in order to ensure the coating suitability of the resin composition for sheet adhesion and the cohesive strength of the resin. Is more preferably 10,000 to 30,000. When the weight average molecular weight is less than 2,000, the internal cohesive force accompanying the entropy elasticity of the resin is insufficient, and cohesive failure may occur, resulting in a decrease in adhesive strength.
• the copolymer (B) When it exceeds 80,000, the copolymer (B) In some cases, the viscosity of the resin composition is high and the coatability may be deteriorated, and the compatibility with the copolymer (A) is deteriorated, and the resin composition for sheet adhesion may become cloudy.
• a weight average molecular weight in the range of 10,000 to 30,000 makes it easy to achieve a balance between coating suitability, cohesive strength and compatibility.
• the ⁇ , ⁇ -unsaturated compound used in the copolymer (B) is not limited as long as it is a known compound, and among them, the ⁇ , ⁇ -unsaturated compound having an active hydrogen group (m- 2) It is preferable to use (except for those that are (m-1)) (hereinafter also simply referred to as (m-2)).
• the active hydrogen group used in the ⁇ , ⁇ -unsaturated compound (m-2) include a hydroxyl group, a sulfonyl group, and a phosphonyl group, and among them, a hydroxyl group is preferably contained.
• the hydroxyl group-containing monomer is For example, 2-hydroxyethyl (2-methyl) propenoate, 1-hydroxypropyl (2-methyl) propenoate, 2-hydroxypropyl (2-methyl) propenoate, 2-methoxyethyl (2-methyl) propenoate, (2-methyl) propenoate 2-ethoxyethyl, (2-methyl) propenoate 2-hydroxybutyl, (2-methyl) propenoate 4-hydroxybutyl, (2-methyl) propenoate polyethene oxide, (2- Hydroxyl group-containing (2-methyl) propenoic acid esters such as methyl) propenoic acid polypropene oxide;
• (2-methyl) propenoic acid polyethene oxide (2-methyl) propenoic acid polypropene oxide, (2-methyl) propenoic acid polytetramethine oxide, (2-methyl) propenoic acid polyhexamethine oxide methyl, etc.
• Polyalkylene glycol-containing (2-methyl) propenoic acid derivatives (2-methyl) propenoic acid derivatives;
• 2-hydroxy-4- [2- (2-methyl) propane-2-enoyloxy] ethoxydiphenylmethanone 2-hydroxy-4- [2-((2-methyl) propane-2-enoyloxy] butoxydiphenyl Methanone, 2,2′-dihydroxy-4- [2- (2-methyl) propane-2-enoyloxy] ethoxydiphenylmethanone, 2-hydroxy-4- [2- (2-methyl) propane-2-enoyloxy ]
• Diphenylmethanone-containing hydroxyl group-containing (2-methyl) propenoic acid derivatives such as ethoxy-4 '-(2-hydroxyethoxy) diphenylmethanone
• a hydroxyl group-containing ⁇ , ⁇ -unsaturated compound 2-hydroxy-4- [2- (2-methyl) propane-2-enoyloxy] ethoxydiphenylmethanone
• 2-hydroxy-4- [2-((2-methyl) propane-2-enoyloxy] butoxydiphenyl Methanone 2,2′-
• sulfonyl group-containing ⁇ , ⁇ -unsaturated compounds include: For example, sulfonyl such as ethenylbenzenesulfonic acid, ethenylsulfonic acid, allylsulfonic acid, allyloxybenzenesulfonic acid, methallylsulfonic acid, methallyloxybenzenesulfonic acid, alkenyl group-containing sulfonic acid compounds such as vinyl sulfuric acid, etc. Examples thereof include ⁇ , ⁇ -unsaturated compounds containing groups.
• Examples of the phosphonyl group-containing monomer in (m-2) include (2-methyl) propenoic acid acid phosphooxyethyl, (2-methyl) propenoic acid acid phosphooxypropyl, and (2-methyl) propene.
• ⁇ , ⁇ -unsaturated compounds having a hydroxyl group are preferable, and among them, 2-hydroxyethyl (2-methyl) propenoate and 4-hydroxybutyl (2-methyl) propenoate are preferable.
• the ⁇ , ⁇ -unsaturated compound (m-2) having an active hydrogen group is contained in an amount of 0.01 to 20 parts by weight in 100 parts by weight of the ⁇ , ⁇ -unsaturated compound used for copolymerization of the copolymer (B).
• the content is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight.
• the amount is less than 0.01 parts by weight, it is difficult to obtain a cohesive force improving effect due to a molecular weight improving effect due to a curing reaction accompanying crosslinking with a functional group contained in a cross-linking agent (C) described later, and a resin composition for sheet adhesion In some cases, the cohesive force in the cured coating film of the product is insufficient, and the adhesive force may not be obtained. When the amount is more than 20 parts by weight, the curing shrinkage due to the curing reaction becomes significant, and sufficient adhesive force may not be obtained. .
• the range of 0.2 to 5 parts by weight is more preferable because the molecular weight accompanying the crosslinking of the cured coating film is improved, not only can the internal cohesive force capable of expressing entropy elasticity be secured, but also the curing shrinkage hardly occurs.
• M-2 may be a single type or a combination of two or more types.
• the other copolymerizable ⁇ , ⁇ -unsaturated compound (m-3) used in copolymer (A) and copolymer (B) is copolymerized with (m-1) and (m-2). Possible ⁇ , ⁇ -unsaturated compounds are used.
• N-alkoxyl-containing acrylamides such as N-methyl-N-methoxyacrylamide and N-methyl-N-methoxymethacrylamide;
• (2-methyl) propenoate polyethene oxide methyl (2-methyl) propenoate polyethene oxide ethyl, (2-methyl) propenoate polyethene oxide propyl, (2-methyl) propenoate polyethene oxide butyl, (2-methyl) propenoate polyethene oxide pentyl, (2-methyl) propenoate polyethene oxide phenyl, (2-methyl) propenoate polyethene oxide phenyl nonyl, (2-methyl) propenoate polyethene oxide phenyl paracumyl , (2-methyl) propenoic acid polypropene oxide methyl, (2-methyl) propenoic acid polypropene oxide ethyl, (2-methyl) propenoic acid polypropene oxide propyl, (2-methyl) propenoic acid polypropene oxide butyrate (2-methyl) propenoic acid polypropene oxide n-pentyl, (2-methyl)
• ethenylbenzenes such as ethenylnaphthalene and ethenylanthracene:
• allyl (2-methyl) propenoate 1-methylallyl (2-methyl) propenoate, 2-methylallyl (2-methyl) propenoate, 1-butenyl (2-methyl) propenoate, (2-methyl) propene 2-butenyl acid, 2-butenyl (2-methyl) propenoate, 1,3-methyl-3-butenyl (2-methyl) propenoate, 2-chloroallyl (2-methyl) propenoate, (2-methyl) propene Acid 3-chloroallyl, (2-methyl) propenoic acid-o-allylphenyl, (2-methyl) propenoic acid 2- (allyloxy) ethyl, (2-methyl) propenoic acid allyl lactyl, (2-methyl) propenoic acid citronellyl, Geranyl (2-methyl) propenoate, rosinyl (2-methyl) propenoate, cinnamyl (2-methyl) propenoate, Le) containing more unsaturated groups such as
• perfluoromethyl (2-methyl) propenoate perfluoroethyl (2-methyl) propenoate, perfluoropropyl (2-methyl) propenoate, perfluorobutyl (2-methyl) propenoate, (2-methyl ) Perfluorooctyl propenoate, trifluoromethyl methyl (2-methyl) propenoate, 2-trifluoromethyl ethyl (2-methyl) propenoate, diperfluoromethyl methyl (2-methyl) propenoate, (2-methyl ) 2-perfluoroethylethyl propenoate, 2-perfluoromethyl-2-perfluoroethylmethyl (2-methyl) propenoate, triperfluoromethylmethyl (2-methyl) propenoate, (2-methyl) propenoic acid 2-perfluoroethyl-2-perfluorobutylethyl, (2-methyl 2-perfluorohexylethyl propenoate, 2-perfluoro
• (2-methyl) propenoic acid glycidyl (2-methyl) propenoic acid (3,4-epoxycyclohexyl) methyl
• (2-methyl) propenoic acid (3-methyl-3-oxetanyl) methyl
• Oxygen atom-containing heterocycle-containing (2-methyl) propenoates such as tetrahydrofurfuryl propenoate;
• ⁇ -unsaturated compound containing an amino group For example, (2-methyl) propenoic acid N-methylaminoethyl, (2-methyl) propenoic acid N-tributylaminoethyl, (2-methyl) propenoic acid N, N-dimethylaminoethyl, (2-methyl) propenoic acid Amino group-containing (2-methyl) propenoic acid esters having a chain amino group such as N, N-diethylaminoethyl;
• a cyclic amino group having one nitrogen atom such as morpholinoethyl (2-methyl) propenoate, pentamethylpiperidinyl (2-methyl) propenoate, tetramethylpiperidinyl (2-methyl) propenoate ( 2-methyl) propenoic acid esters;
• 3-pyrroline-2,5-dione 1-methyl-1H-pyrrole-2,5-dione, 1-ethyl-1H-pyrrole-2,5-dione, 1-propyl-1H-pyrrole-2, 5-dione, 1-butyl-1H-pyrrole-2,5-dione, 1-octyl-1H-pyrrole-2,5-dione, 1-dodecyl-1H-pyrrole-2,5-dione, 1-stearyl- Nitrogen-containing 3-pyrroline-2,5 such as 1H-pyrrole-2,5-dione, 1-phenyl-1H-pyrrole-2,5-dione, 1-cyclohexyl-1H-pyrrole-2,5-dione -Dione derivatives;
• di (2-methyl) propenoic acid ethene oxide di (2-methyl) propenoic acid triethene oxide, di (2-methyl) propenoic acid tetraethene oxide, di (2-methyl) ) Propenoic acid polyethene oxide, di (2-methyl) propenoic acid propene oxide, di (2-methyl) propenoic acid dipropene oxide, di (2-methyl) propenoic acid tripropene oxide, di (2-methyl) propenoic acid Polypropene oxide, di (2-methyl) propenoic acid butene oxide, di (2-methyl) propenoic acid pentenoxide, di (2-methyl) propenoic acid 2,2-dimethylpropyl, di (2-methyl) propenoic acid hydroxy Pivalyl hydroxypivalate (common name: Manda), di (2-methyl) propenoic acid Roxypivalyl hydroxypivalate dicaprolactonate, 1,6
• ethenyl phenyl pentyl ether ethenyl phenyl hexyl ether, ethenyl phenyl heptyl ether, ethenyl phenyl octyl ether, ethenyl phenyl nonyl ether, ethenyl phenyl decyl ether, ethenyl phenyl undecyl ether, ethenyl phenyl dodecyl ether Ethenyl phenyl tridecyl ether, ethenyl phenyl tetradecyl ether, ethenyl phenyl pentadecyl ether, ethenyl phenyl hexadecyl ether, ethenyl phenyl heptadecyl ether, ethenyl phenyl octa
• isopropenyl phenylmethyl butyl ether isopropenyl phenyl methyl pentyl ether, isopropenyl phenyl methyl hexyl ether, isopropenyl phenyl methyl heptyl ether, isopropenyl phenyl methyl octyl ether, isopropenyl phenyl methyl nonyl ether, isopropenyl phenyl methyl decyl ether, Isopropenyl phenylmethyl undecyl ether, isopropenyl phenyl methyl dodecyl ether, isopropenyl phenyl methyl tridecyl ether, isopropenyl phenyl methyl tetradecyl ether, isopropenyl phenyl methyl pentadecyl ether, isopropenyl phenyl methyl hex
• ethenylbenzene, ⁇ -isopropenylbenzene, ⁇ -isopropenylbenzene 1-methylethenylbenzene, 2-methylethenylbenzene, 3-methylethenylbenzene, 1-butylethenylbenzene, 1-chloro- Aromatic ethenyls such as 4-isopropenylbenzene;
• tetra (ethene oxide) ethenylphenyl ether methyltetra (etheneoxide) ethenylphenylether, ethyltetra (etheneoxide) ethenylphenylether, propyltetra (etheneoxide) ethenylphenylether, n-butyltetra (ethenoxide) ) Ethenyl phenyl ether, n-pentyltetra (ethene oxide) ethenyl phenyl ether, tetra (propene oxide) ethenyl phenyl ether, methyl tetra (propene oxide) ethenyl phenyl ether, ethyl tetra (propene oxide) ethenyl phenyl ether, Propoxytetra (propene oxide) ethenyl ether,
• poly (ethene oxide) isopropenyl phenyl ether methyl poly (ethene oxide) isopropenyl phenyl ether, ethyl poly (ethene oxide) isopropenyl phenyl ether, poly (propene oxide) isopropenyl phenyl ether, methyl poly (propene oxide) isopropenyl phenyl Ether, ethyl poly (propene oxide) isopropenyl phenyl ether, poly (ethene oxide) isopropenyl benzyl ether, methyl poly (ethene oxide) isopropenyl benzyl ether, ethyl poly (ethene oxide) isopropenyl benzyl ether, poly (propene oxide) isopropenyl benzyl ether Ether, methylpoly (propene oxide) isopropenyl benzil Isopropenyl
• Fluorine-containing ethenyls such as, for example, perfluoroethene, perfluoropropene, perfluoro (propyl ethenyl ether), ethenylidene fluoride;
• triethyloxysilyl group-containing ethenyls such as ethenyltrimethoxysilane and ethenyltriethoxysilane;
• Nitrile group-containing ethenyl such as 2-propenenitrile, 2-methyl-2-propenenitrile, 2-cyanoethyl (2-methyl) propenoate;
• glycidyl group-containing ethenyl esters such as glycidyl cinnamate, allyl glycidyl ether, ethenylcyclohexene monooxirane, 1,3-butadiene monooxirane;
• dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene;
• Examples include, but are not limited to, chloroethene, 1,1-dichloroethene, allyl chloride, allyl alcohol, and the like.
• a copolymer of an ⁇ , ⁇ -unsaturated compound having at least one propane-2-enoyl group and 2-methylpropane-2-enoyl group in the molecule wherein ⁇
• ⁇ also included are high molecular weight type polymerizable copolymers having ⁇ -unsaturated double bonds, so-called macromonomers.
• the copolymer (A) and copolymer (B) in the present invention are based on 100 parts by weight of the total of the various ⁇ , ⁇ -unsaturated compounds (m-1) to (m-3) as described above.
• polymerization initiators examples include 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutanenitrile), 1,1'-azobis (cyclohexane 1-carbonitrile) 2,2'-azobis (2,4-dimethylpentanitrile), 2,2'-azobis (2,4-dimethyl-4-methoxypentalonitrile) and dimethyl 2,2'-azobis (2-methyl) Propionate), 4,4′-azobis (4-cyanopentanoic acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazoline-2 And azo compounds such as -yl) propane].
• organic peroxides such as rate, (3,5,5-trimethylhexanoyl) peroxide, dipro
• mercaptans such as lauryl mercaptan and n-dodecyl mercaptan
• chain transfer agents such as ⁇ -methylstyrene dimer and limonene may be used.
• 2,2′-azobisisobutyronitrile, dimethyl 2,2′-azobis (2-methylpropionate), dibenzoyldioxidane, and tert-butyl are used.
• Perbenzoate, tert-butyl peroxypivalate, tert-hexyl peroxypivalate, octanoyl peroxide, lauroyl peroxide, tert-butylperoxy-2-ethylhexanoate are preferred.
• examples of the solvent include aromatic solvents such as methylbenzene and 1,2-dimethylbenzene; ethanol, propan-2-ol Alcohol solvents such as 1-butanol; ether solvents such as 1-methoxy-2-propanol, (2-methoxymethylethoxy) -propanol 2-ethoxyethanol, 2-butoxyethanol; ethyl ethanoate, butyl ethanoate, Ester solvents such as 2-ethoxyethanol acetate; ketone solvents such as 2-propanone, 2-butanone, 4-methyl-2-pentanone and 2,4-pentadione; organic solvents such as amide solvents such as dimethylformamide
• aromatic solvents such as methylbenzene and 1,2-dimethylbenzene
• ethanol propan-2-ol Alcohol solvents
• ether solvents such as 1-methoxy-2-propanol, (2-methoxymethylethoxy) -propanol 2-ethoxyethanol, 2-butoxyethanol
• the amount of the solvent includes the polymerization conditions, the composition of the ⁇ , ⁇ -unsaturated compounds (m-1) to (m-3), the viscosity and concentration of the resulting copolymer (A) and copolymer (B), etc. May be appropriately determined in consideration of the above.
• the polymerization conditions for producing the copolymer (A) and the copolymer (B) may be appropriately set according to the polymerization method, and are not particularly limited.
• the polymerization temperature is preferably room temperature to 150 ° C, more preferably 40 to 120 ° C.
• the reaction time may be appropriately set so that the polymerization reaction of the ⁇ , ⁇ -unsaturated compounds (m-1) to (m-3) components is completed.
• crosslinking agent (C) As the crosslinking agent (C), those capable of undergoing a curing reaction with the copolymer (A) and the copolymer (B) can be used without limitation.
• the functional groups (carboxyl group, amide group, carbonyl group and N-alkoxy group) contained in (m-1)
• a crosslinking agent that undergoes a curing reaction with one or more functional groups selected from the group consisting of alkyl groups is preferred.
• (m-2) is used as the ⁇ , ⁇ -unsaturated compound for the copolymer (B)
• a crosslinking reaction that reacts with a functional group having an active hydrogen group contained in (m-2).
• Agents are preferred.
• a crosslinking agent (C) can be used individually or in combination.
• a crosslinking agent capable of undergoing a curing reaction with both the copolymer (A) and the copolymer (B)
• a copolymer (B And a crosslinking agent (C) capable of undergoing a curing reaction alone.
• the crosslinking agent (C) plays the role of improving the molecular weight of the cured coating film of the resin composition for sheet adhesion, improving the internal cohesive force that develops energy elasticity, and improving the interaction with the substrate surface described later. The effect can also be expected. Furthermore, for a base material subjected to physical treatment such as corona discharge treatment or chemical treatment modified with an acid or the like, the reactive functional group in the cross-linking agent (C) is chemically reacted with the base material. It is also possible to develop a strong interaction between the copolymer (A) and the copolymer (B) and the substrate.
• crosslinking agent (C) it becomes possible to form a firm cured coating film, and the crosslinking agent (C) that expresses the energy elasticity of the expansion and contraction movement of the substrate accompanying a rapid environmental change. Can be suppressed.
• crosslinking agent (C) examples include a polyisocyanate compound (c-1), a polyfunctional epoxy compound (c-2), a metal chelate compound (c-3), and a polycarbodiimide compound (c-4) (more preferably , High molecular weight polycarbodiimide compounds), N-methylol group-containing compounds, aziridine compounds (c-5) (more preferably, polyfunctional aziridine compounds), and the like.
• a carboxyl group, an amide group, a carbonyl group and an N-alkoxyalkyl group in the copolymer (A), and a copolymer are used in order for the curing reaction accompanying the crosslinking of the crosslinking agent (C) to act effectively.
• a compound having two or more functional groups capable of reacting with the active hydrogen group in (B) in the molecule is preferably used.
• the polyisocyanate compound is preferably used because it is excellent in the adhesiveness of the resin composition for sheet adhesion after the curing reaction.
• the polyisocyanate compound (c-1) is not particularly limited as long as it is a compound having a plurality of isocyanate groups in the molecule.
• polyisocyanate compounds include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenylmethane trisene.
• Polyisocyanate compounds such as isocyanate and polymethylene polyphenyl isocyanate, adducts of these polyisocyanate compounds and polyol compounds such as 2- (hydroxymethyl) -2-ethylpropane-1,3-diol, Burettes and isocyanurates, and these polyisocyanate compounds
• polyether polyols or polyester polyols polypropene acid alkyl polyols, polybutadiene polyols, adducts, etc. and polyisoprene polyol and the like.
• Hexamethylene diisocyanate isocyanurate trimer, hexamethylene diisocyanate burette (c-1-1), adduct of isophorone diisocyanate and 2- (hydroxymethyl) -2-ethylpropane-1,3-diol, isophorone Diisocyanate isocyanurate trimer (c-1-2) is preferred.
• the polyfunctional epoxy compound (c-2) is not particularly limited as long as it is a compound having a plurality of epoxy groups in the molecule.
• the polyfunctional epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A / epichlorohydrin type epoxy resin, N, N, N ′, N Examples include '-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N-diglycidylaniline, N, N-diglycidyltoluidine, and the like.
• Examples of the high molecular weight polycarbodiimide compound include Nisshinbo's Carbodilite series. Among these, carbodilite V-01, 03, 05, 07, and 09 are preferable because of excellent compatibility with organic solvents.
• polyfunctional aziridine compound examples include 2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate], 4,4′-bis (ethyleneiminocarbonylamino) diphenylmethane, and the like.
• Examples of the metal chelate compound (c-3) include polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium, 2,4-pentadione and ethyl. And a coordination compound with -3-oxobutanoate.
• the crosslinking agent (C) can be used alone or in combination.
• the crosslinking agent (C) is preferably added in an amount of 0.1 to 30 parts by weight, more preferably 1 to 25 parts by weight, based on a total of 100 parts by weight of the copolymer (A) and the copolymer (B). Parts, more preferably 2 to 15 parts by weight. If the amount is less than 0.1 parts by weight, the amount of the crosslinking agent (C) added is small, the effect of improving the molecular weight of the cured coating film due to the curing reaction cannot be obtained, and the energy elasticity is insufficient, resulting in insufficient cohesive force , Adhesive strength may decrease.
• the amount exceeds 30 parts by weight there is a concern that excess crosslinking agent (C) may remain unreacted in the sheet-adhesive resin composition, resulting in a decrease in adhesive strength.
• the cross-linking agent (C) remaining during the durability test causes a curing reaction accompanying the cross-linking, and the energy elasticity of the resin composition for sheet bonding is too high, or the wettability to the substrate. May deteriorate or deteriorate.
• the range of 2 to 15 parts by weight is more preferable from the viewpoints of the effect of improving the cohesive force and the effect of reducing the residual crosslinking agent.
• the resin composition for sheet bonding of the present invention comprises a copolymer (A), a copolymer (B), and a cross-linking agent (C).
• the copolymer (A) and the copolymer (B) , And a crosslinking agent (C) may be mixed at the time of use, and a so-called three-component mixed sheet resin composition may be used, or the copolymer (A) and the copolymer (B) are mixed in advance.
• the copolymer mixture and the crosslinking agent (C) may be mixed at the time of use, which may be a so-called two-component mixed resin composition for sheet adhesion, and depending on the use conditions, the main resin and the crosslinking agent ( C) may be a pre-mixed one-component type resin composition for sheet bonding. Moreover, you may use a copolymer (A), a copolymer (B), and a crosslinking agent (C) in multiple types each independently.
• the first solution when used as a two-component mixed type, includes a copolymer (A), a copolymer (B), an organic solvent, and other additives, and the second solution includes a crosslinking agent ( C), including organic solvents and other additives.
• A copolymer
• B copolymer
• C crosslinking agent
• the copolymer (A) is preferably contained in an amount of 30 to 95 parts by weight, more preferably 40 to 80 parts by weight, still more preferably 50 parts by weight. It is preferable to include ⁇ 70 parts by weight.
• the amount is less than 30 parts by weight, the cohesive strength of the copolymer (B) becomes remarkable, the wettability of the resin composition for sheet adhesion is lost, and the adhesion to the film during lamination is reduced.
• the cohesive force in the cured coating film of the sheet-adhesive resin composition is insufficient, tends to cohesive failure at the time of peeling, and the adhesive force may decrease.
• 50 to 70 parts provide a good balance between the wettability and the cohesive force of the cured coating film, and often have high adhesive strength.
• the resin composition for sheet adhesion of the present invention is a cured coating film that does not affect various environmental changes accompanying the curing reaction accompanying the crosslinking of the copolymer (A), the copolymer (B), and the crosslinking agent (C). Can be provided.
• the function of the copolymer (A) is a relatively low Tg and high molecular weight form, so that it exhibits effective wettability with respect to various substrates, and develops stress relaxation with a curing reaction with a crosslinking agent.
• the copolymer (B) has a high Tg and low molecular weight form, and therefore exhibits an entropy elasticity that follows the expansion and contraction movement of the base material accompanying a gradual environmental change.
• the cross-linking agent (C) expresses energy elasticity that suppresses rapid expansion and contraction of the base material in order to express a rigid structure accompanying self-reaction in addition to the curing reaction accompanying both copolymers and cross-linking. is there.
• the cured coatings associated with these crosslinks form an interpenetrating network structure (IPN: Interpenetrating polymer network) that expresses each feature independently, and a microscopic multilayer structure.
• IPN Interpenetrating polymer network
• the resin composition for sheet adhesion of the present invention includes a silane coupling agent, a tackifier, a leveling agent, a phosphorus-based or phenol-based antioxidant within the range not departing from the gist of the present invention.
• Various additives such as an ultraviolet stabilizer, a metal deactivator, a flame retardant, a plasticizer, and an organic / inorganic pigment can be blended.
• a phosphoric acid compound such as phosphorous is used in order to improve the metal adhesion of the resin composition for sheet adhesion of the present invention.
• Acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, esters thereof and the like can be added.
• seat adhesion of this invention is preferably used as a bonding agent for solar cell protection sheet manufacture, and is a solar cell laminated sheet anchor that is thermocompression bonded at a high temperature of 100 ° C. or higher after coating for 30 minutes or more. It can also be used as a coating agent. In that case, in order to eliminate the tack after coating, minerals such as talc, diatomaceous earth, calcium carbonate, feldspar, quartz and the like and antiblocking agents such as silica and PMMA (methyl 2-methyl-2-propenoate) beads are used. It is preferable to add.
• a known additive for sheet adhesive resin composition can be blended without limitation without departing from the gist of the present invention.
• a known leveling agent or antifoaming agent can be added to the resin composition for sheet adhesion.
• leveling agent examples include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyester-modified hydroxyl group-containing polydimethylsiloxane, polyetherester-modified hydroxyl group-containing polydimethylsiloxane, and polyether-modified polymethyl.
• examples include alkylsiloxanes, (2-methyl) propenoic acid alkyl ester copolymers, lecithin, and mixtures thereof.
• antifoaming agent examples include known resins such as silicone resins, copolymers of alkylethenyl ethers and (2-methyl) propenoic acid alkyl esters, or mixtures thereof.
• resins such as silicone resins, copolymers of alkylethenyl ethers and (2-methyl) propenoic acid alkyl esters, or mixtures thereof.
• a leveling agent and an antifoaming agent are added, one type of compound may be used independently, or two or more types may be used in any combination.
• a known phosphorus-based or phenol-based oxidation is used for the purpose of further suppressing deterioration yellowing of the resin composition for sheet bonding due to ultraviolet rays or heat such as the sun over time.
• An inhibitor, an ultraviolet stabilizer, and a metal deactivator can be blended in the resin composition for sheet adhesion. These may be used alone or in any combination of two or more.
• the phosphorus-based or phenol-based antioxidant, UV stabilizer, and metal deactivator used in the present invention are in the range of 0.05 to 20 parts by weight with respect to 100 parts by weight of the solid content of the copolymer (A). The amount is preferably 0.1 to 10 parts by weight.
• the addition amount is less than 0.05 weight, there is a possibility that a sufficient deterioration yellowing suppressing effect may not be obtained, and if it is more than 20 parts by weight, the adhesive force of the resin composition for sheet adhesion is greatly deteriorated. There is a fear.
• the nonvolatile content (hereinafter also referred to as solid content) of the resin composition for sheet adhesion of the present invention is preferably in the range of 10 to 50% by weight.
• attachment of this invention can adjust solid content using the solvent which was illustrated above.
• Examples of the solvent used in the sheet adhesive resin composition include ester solvents such as ethyl ethanoate, butyl ethanoate, and 2-ethoxyethanol acetate; 2-propanone, 2-butanone, 4-methyl-2-pentanone Ketone solvents such as 2,4-pentadione; aromatic solvents such as methylbenzene and 1,2-dimethylbenzene; halogenated hydrocarbons such as methylene chloride and ethylene chloride; amide solvents such as dimethylformamide Can be mentioned.
• ester solvents such as ethyl ethanoate, butyl ethanoate, and 2-ethoxyethanol acetate
• 2-propanone, 2-butanone, 4-methyl-2-pentanone Ketone solvents such as 2,4-pentadione
• aromatic solvents such as methylbenzene and 1,2-dimethylbenzene
• halogenated hydrocarbons such as methylene chloride and ethylene chloride
• seat adhesion is demonstrated.
• a generally used method can be used. For example, a sheet adhesive resin composition is applied to one side of one film with a comma coater or a dry laminator, the solvent is stripped off as necessary, and the other film to be laminated is bonded to room temperature or heated. What is necessary is just to make it harden-react below and to make it adhere
• the resin composition for sheet adhesion applied to the film is preferably about 1 to 50 g / m 2 .
• attachment which concerns on this invention can be used for all or one part at the time of bonding between the films of each layer and adhere
• the resin composition for sheet bonding of the present invention is produced by applying the sheet bonding resin composition to a film, drying it, laminating the film, and curing the laminate at 20 to 60 ° C. for several days. While performing the curing process (dark reaction process), the curing reaction of the copolymer (A) and the copolymer (B) with the crosslinking agent (C) is advanced, and the interaction with the laminated film is improved. Each viscoelastic behavior can be controlled.
• the laminated body of this invention can be formed by laminating
• a base material (G) As a base material (G), a plastic film (a plastic sheet is included), metal foil, etc. can be mentioned, It selects suitably from the characteristic calculated
• insulating properties using a polyester film, which will be described later, insulating properties, using a fluorine film, weather resistance, polyolefin film, plastic film on which metal oxide or non-metal inorganic oxide is deposited, metal foil
• the water vapor barrier property can be imparted by using it.
• plastic film examples include polyester resin films such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN); Fluorine-based materials such as polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, polyethylene tetrafluoroethylene, polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer Resin film; Polyolefin films such as polyethylene resin films such as low density polyethylene (LDPE) and linear low density polyethylene (LLDPE), and polypropylene resin films; Examples thereof include a polyvinyl chloride resin film, a polycarbonate resin film, a polysulfone resin film, and a poly (2-methyl) propenoic acid resin film.
• PET polyethylene terephthalate
• PBT poly
• the above plastic film has a surface with physical treatment such as corona discharge, plasma treatment, flame treatment, etc., chemical treatment that modifies the film surface with acid or alkali, etc.
• a surface with physical treatment such as corona discharge, plasma treatment, flame treatment, etc.
• chemical treatment that modifies the film surface with acid or alkali, etc.
• the resin composition for sheet adhesion such as a film having an increased surface area, those that have been subjected to easy adhesion treatment can be suitably used.
• plastic films on which metal oxides or non-metal inorganic oxides are deposited include, for example, oxides such as silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, and yttrium. The thing vapor-deposited on the film is mentioned.
• PET polyethylene terephthalate
• PET polyethylene terephthalate
• Metal foil includes aluminum foil and copper foil.
• a film colored in black or white can be used for the purpose of improving the design property or improving the light reflectance and improving the conversion efficiency of the solar cell.
• the laminated body has a multi-layer structure
• a polyester resin film or a fluorine resin film is easily bonded as a method for developing the excellent adhesive force of the resin composition for sheet bonding according to the present invention. It is possible to enhance the interaction with the base material in the heating and solvent removal process by coating from the film surface that is extremely difficult to adhere, such as an olefin base material such as polypropylene Therefore, it is used more preferably.
• the manufacturing method and configuration of the solar cell protective sheet adopt various manufacturing methods and configurations depending on the purpose and needs such as heat resistance, weather resistance, water vapor permeability, and electrical insulation. it can.
• Polyester resin films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polycarbonate resin films, and polyolefin films to prevent output degradation due to the influence of water on solar cells, and water vapor barrier properties
• Laminated metal film such as plastic film or aluminum foil deposited with metal oxide or non-metal inorganic oxide, and polyolefin film and fluorine resin film with good weather resistance to prevent appearance defects due to light deterioration Solar cell protection sheet made of Arbitrariness.
• the sheet-bonding resin composition of the present invention is characterized by having excellent weathering yellowing and high transparency. Even when the solar cell protective sheet of the present invention is used as a protective sheet on the light-receiving surface side, the light transmittance is not deteriorated, and excellent power generation efficiency can be exhibited. Therefore, it can be used as a surface protection sheet and a back surface protection sheet.
• Production Example 1 (Synthesis Example A-1) ⁇ Production of copolymer (A)> A polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, a polymerization reactor and a dropping device of a polymerization reaction apparatus equipped with a nitrogen introduction tube, from the group consisting of the following monomer, carboxyl group, amino group, and amide group An ⁇ , ⁇ -unsaturated compound (m-1), an ⁇ , ⁇ -unsaturated compound (m-3), a polymerization initiator, and a solvent having a selected functional group were charged in the following ratios.
• the copolymer (A-1) had a weight average molecular weight of 82,000 and a molecular weight distribution of 2.3 according to the measurement method described later.
• the calculated Tg was ⁇ 35.2 ° C.
• Synthesis Examples A-2 to 11 Synthesis was carried out in the same manner as in Synthesis Example 1 except that the raw materials and preparation parts shown in Table 1 were used, and resin solutions of copolymers (A-2) to (A-11) were obtained.
• ⁇ ⁇ -unsaturated compound (m-1) having one or more functional groups selected from the group consisting of carboxyl group, amide group, carbonyl group and N-alkoxyalkyl group”: (M-1-1) propenoic acid, (M-1-2) 2-methyl-2-propenoic acid, (M-1-3) 2-methylenesuccinic acid, (M-1-4) 2-propenamide, (M-1-5) 2- (1,3-dioxobutoxy) ethyl 2-methyl-2-propenoate, (M-1-6) N-methoxymethyl-2-propenamide; “Other copolymerizable ⁇ , ⁇ -unsaturated compound (m-3) (except (m-1) and (m-2))”: (M-3-2) ethyl propenoate, (M-3-3) n-butyl propenoate, (M-3-4) 2-ethylhexyl propenoate (M-3-5
• Production Examples 12 to 20 (Synthesis Examples B-1 to 9) Synthesis was carried out in the same manner as in Production Example 1 except that the raw materials and preparation parts shown in Table 2 were used, and resin solutions of copolymers (B-1) to (B-9) were obtained.
• Production Examples 21-30 Synthesis was carried out in the same manner as in Production Example 1 except that the raw materials and preparation parts shown in Table 3 were used, and resin solutions of copolymers (H-1) to (H-10) were obtained.
• Example 1 To 25 parts by weight of the copolymer (A-1) obtained in Synthesis Example 1, 75 parts by weight of the copolymer (B-1) obtained in Synthesis Example 10 was added and stirred. Thereafter, (c-1 (1)) prepolymer of polymethylene polyphenyl isocyanate, Sumidur Bayer Urethane Sumidur E21-1 (NCO%: 16.0% solid content 100%) as a crosslinking agent (C) 13. 7 parts by weight, epoxy compound (c-2): 13.2 parts by weight of N, N, N ′, N′-tetraglycidyl-m-xylenediamine was added. In order to obtain a nonvolatile content of about 30%, ethyl acetate was added and stirred well to obtain a resin composition for sheet bonding (S-1).
• Viscosity increase rate is 2 times or more in 1 hour of addition. There are practical problems. In Example 1, the rate of increase in viscosity at 8 hours was 1.3 times, and the rate of increase in viscosity at 24 hours was 2.4 times.
• a sheet of polyester film (Toray Industries, Lumirror X-10S, thickness 50 ⁇ m) subjected to corona treatment (hereinafter referred to as “corona treatment surface as corona treatment + film name”) is a sheet.
• the adhesive resin composition was applied to the sheet adhesive resin composition (S-1) by a dry laminator at a dry coating amount of 5 to 7 g / m 2 .
• the laminated body 1 was obtained by making it age at 50 degreeC for 96 hours.
• laminate 2 [corona-treated polyester film / sheet adhesive resin composition layer / JIS1N30 soft aluminum foil]
• laminate 3 [corona-treated polyester film / sheet adhesive resin composition layer / silicon dioxide-deposited PET] -Based film (Mitsubishi Resin Co., Ltd., trade name: Tech Barrier)]
• laminate 4 Polyyester-based film (Toray Industries, Lumirror X-10S, untreated surface with a thickness of 50 ⁇ m) / sheet adhesive resin composition layer / ETFE (Ethylene-tetrafluoroethylene copolymer) film (Asahi Glass Co., Ltd .: FluonETFE Film, thickness 25 ⁇ m)]
• laminate 5 [corona-treated polyester film / resin composition layer for sheet adhesion / corona-treated LLDPE film (Futamura) Chemical company LL-XUM30N # 30)]
• laminate 6 [ETFE (ethylene-tetrafluoroethylene copolymer weight) Body) film (A
• Example 1 The state after curing of the obtained laminate 1 was visually observed and evaluated in three stages. a: A smooth coated surface was obtained. Very good. b: Slight repellency and foaming are observed at the end of the coated surface, but good. c: Repelling, foaming, white turbidity, and streaks are observed on the coated surface, which is problematic in practical use. In Example 1, a smooth coated surface was obtained and was very good.
• ⁇ Peeling strength test before curing The laminate 1 before curing is cut into a size of 200 mm ⁇ 15 mm, left to stand in an environment of 25 ° C. and 65% humidity for 6 hours, and subjected to the test method of ASTM-D1876-61. Similarly, a 180 ° peel test was performed at a load speed of 100 mm / min in an environment of 25 ° C. and a humidity of 65% using a tensile tester, and evaluation was performed in four stages.
• aa Peel strength is 2 N / 15 mm or more. Excellent adhesion.
• a Peel strength of 1 N / 15 mm or more and less than 2 N / 15 mm. Excellent adhesion.
• Example 1 Peel strength 3N / 15mm or more and less than 5N / 15mm. Adhesiveness is slightly insufficient and there are practical problems. c: Peel strength is less than 3 N / 15 mm. Adhesive failure There are practical problems. In addition, although Example 1 was as showing in Table 3, it was a result that it was excellent in adhesiveness.
• Example 1 Peel strength of 5 N / 15 mm or more and less than 8 N / 15 mm. Excellent adhesion.
• b Peel strength 3N / 15mm or more and less than 5N / 15mm. Adhesiveness is slightly insufficient and there are practical problems. However, since the wet heat 3000 hour test was overestimated, it was judged that it could be used even in the b evaluation.
• c Peel strength is less than 3 N / 15 mm. Adhesive failure There are practical problems.
• Example 1 is as having shown in Table 4, in the laminated body 5, it was a result that peeling strength is 5.6 N / 15mm and it is excellent in adhesiveness, and it is excellent in the moisture-heat test.
• Example 1 is as having shown in Table 3, it turned out that (DELTA) b value is 5.1 and is excellent in weathering yellowing.
• Example 2 to 19 Resin compositions for sheet adhesion (S-2) to (S-19) were obtained in the same manner as in Example 1 except that the raw materials and preparation amounts shown in Tables 4 and 5 were used. It was. The result of having implemented evaluation similar to Example 1 is shown.
• Comparative Example 1 corresponds to the example of Japanese Patent No. 4824544 of Patent Document 4
• Comparative Example 11 corresponds to the example of Japanese Patent Application Laid-Open No. 2010-263193 of Patent Document 7
• Comparative Example 12 corresponds to the Example of Japanese Patent Application Laid-Open No. 2012-142349 of Patent Document 8. To do.
• the resin compositions for sheet adhesion of the examples are excellent in peel strength before curing, peel strength after curing, and peel strength after wet heat resistance test, and maintain adhesive strength over a long period of time.
• This is because by blending resins with different resins Tg, the pre-curing adhesion and the wettability to the base material during curing are improved by the low glass transition point copolymer (A), and the cohesive strength of the coating film is improved.
• the copolymer (B) having a high glass transition point and energy elasticity by the crosslinking agent (C) and further crosslinking the copolymers (A) and (B) with the crosslinking agent (C).
• JIS C178917 (environmental test method and durability test method for crystalline solar cell module) stipulates a moisture resistance test B-2 to endure for 1000 hours at 85 ° C and 85% humidity. It is known as a particularly harsh test method. In this example, it is shown that the adhesive strength can be maintained over a long period of more than 1000 hours and over 3000 hours, and it can be said that the resin composition for sheet bonding of the present invention has sufficient long-term wet heat resistance.
• the resin composition for sheet adhesion according to the present invention is a multilayer laminate material for outdoor industrial applications such as buildings (barrier material, outer wall material, roofing material, solar cell panel material (solar cell protection sheet), window material, outdoor flooring material,
• a strong adhesive strength can be provided as a resin composition for adhering sheets for use in proof protection materials, automobile members, and the like.
• Comparative Example 1 and Comparative Example 2 are examples in which the copolymer (B) is not added to the copolymer (A).
• Comparative Example 1 the influence of the acceleration of the isocyanate group curing reaction by the acid is strong, The pot life was bad and the result was that coating was impossible.
• Comparative Example 2 coating was possible, but the cohesive force was insufficient due to the low Tg of the resin, and sufficient peel strength was not obtained.
• Comparative Example 3 was an example in which coating was attempted only with the copolymer (B). Since the resin Tg was too high, peeling of the film occurred at the time of bonding, and bonding was impossible. From the results of Comparative Examples 1, 2, and 3, it is difficult to ensure high adhesive strength with the coated product of the copolymer (A) and the copolymer (B) alone.
• Comparative Examples 4 to 6 are examples in which the glass transition point of the copolymer (A) is lower than the scope of this right. If the glass transition temperature of the copolymer (A) is too low, the cohesive strength is insufficient and the adhesive strength cannot be obtained. Moreover, although the comparative example 4 is an Example of patent document 4, since the active hydrogen is not included in a copolymer (B), the hardening reaction accompanying bridge
• Comparative Example 7 is an example in which the glass transition point of the copolymer (A) is high.
• the glass transition point of the copolymer (A) is high, the wettability at the time of bonding is insufficient, and a gap is generated between the film and the coating film. For this reason, it is difficult to increase the interaction between the coating film and the film at the time of curing, and thus the adhesive strength after curing cannot be obtained.
• Comparative Example 8 is an example in which the glass transition point of the copolymer (B) is low.
• the glass transition point of the copolymer (B) is low, there is no problem in the adhesive strength at the time of bonding, but the cohesive force of the entire coated film after curing is insufficient and the adhesive strength cannot be obtained.
• Comparative Example 9 is an example where the glass transition point of the copolymer (B) is high.
• the glass transition point of the copolymer (B) is too high, the compatibility with the copolymer (A) tends to be deteriorated, and the coating surface becomes rough. As a result, oxidation is accelerated in the weathering yellowing test, and yellowing occurs.
• the wettability after coating was low and the adhesive strength before curing was insufficient, the adhesive strength after curing was not obtained. From the above Comparative Examples 4 to 9, it was estimated that there was an optimum value for the glass transition point of the copolymer (A) and the copolymer (B).
• Comparative Example 10 is an example in which no cross-linking agent (C) was added. Since the crosslinking agent (C) was not used, the effect of improving the energy elasticity of the coating film due to the curing reaction with the crosslinking agent (C) could not be obtained, resulting in insufficient adhesive strength.
• Comparative Example 11 and Comparative Example 12 are examples in which the copolymer (A) and the copolymer (B) are designed with a single resin without mixing.
• Comparative Example 11 is an example of Patent Document 7 and Comparative Example 12 is an example of Patent Document 8.
• Comparative Example 11 since the glass transition point of the resin was too high, the wettability at the time of bonding was insufficient, and as in Comparative Example 3, the adhesive strength was not obtained.
• the resin design Tg was low, the adhesive strength was low, and the heat resistance was low, resulting in a decrease in adhesive strength during the wet heat test, which was not at a practical level.
• attachment which concerns on this invention can be utilized suitably for joining of the same or different raw material.
• it is suitable for joining a multilayer laminate of a plastic material and a metal material, joining plastic films, and joining metal films.
• adhesive strength can be ensured with a thin film, and the weight reduction of a solar cell protection sheet is attained.
• it can be used for multi-layer laminates for outdoor industrial applications such as buildings (for example, barrier materials, outer wall materials, roof materials, solar panel materials (solar cell protection Sheet), window material, outdoor flooring material, lighting protection material, automobile member, etc.).
• the resin composition for sheet bonding according to the present invention exhibits high adhesive strength particularly between laminates including a surface-treated layer of a plastic film, but is not subjected to surface untreated film (including surface untreated plastic film). It can be suitably applied to.

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