Classifications

• • 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
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
  • B65D65/38—Packaging materials of special type or form
  • B65D65/40—Applications of laminates for particular packaging purposes

Definitions

• the present invention relates to a laminate that has excellent recyclability and heat resistance and is suitable for food packaging, and a packaging material obtained using the laminate.
• Packaging materials used for packaging food and daily necessities are usually made of a heat-sealable film such as unstretched polyethylene film or polypropylene film, and a resin film with excellent heat resistance and strength such as polyester film or nylon film, combined with an adhesive.
• Patent Documents 1 and 2 On the other hand, in recent years, with increasing calls for building a recycling-oriented society, attempts have been made to recycle and use packaging materials. However, in the above-mentioned laminate in which different types of resin films are bonded together, it is difficult to separate the resins for each type, and the laminate is not suitable for recycling.
• a stretched polyolefin film such as stretched polypropylene or stretched polyethylene film is used as the outer layer when viewed from the contents, and an unstretched polypropylene film or low density film is used as the inner layer (sealant film). It is conceivable to use a polyethylene film or the like. Since the olefin resin occupies most of the entire laminate, such a laminate has excellent recyclability compared to a laminate using different types of base materials.
• the present invention was made in view of this background, and aims to provide a laminate with excellent recyclability and heat resistance, and a packaging material using the laminate.
• the present invention comprises a composite resin (A) comprising a heat-sealing layer, a stretched polyolefin film, and a coat layer in this order, and the coat layer has a polysiloxane segment (a1) and a vinyl polymer segment (a2).
• the present invention relates to a laminate including:
• the laminate of the present invention it is possible to provide a laminate and packaging material with excellent heat resistance and recyclability.
• the laminate of the present invention includes a heat seal layer, a stretched polyolefin film, and a coat layer in this order.
• stretched polyolefin film examples include high-density polyethylene film (HDPE), uniaxially stretched polyethylene film (MDOPE), biaxially stretched polyethylene film (OPE), and biaxially stretched polypropylene film (OPP).
• HDPE high-density polyethylene film
• MDOPE uniaxially stretched polyethylene film
• OPE biaxially stretched polyethylene film
• OPP biaxially stretched polypropylene film
• the thickness of the stretched polyolefin film can be adjusted as appropriate depending on the purpose, but from the viewpoint of the balance between mechanical strength and processability, it is preferably 5 ⁇ m or more and 300 ⁇ m or less. More preferably, it is 7 ⁇ m or more and 100 ⁇ m or less.
• the stretched polyolefin film may be surface-treated. Thereby, adhesion between adjacent layers can be improved.
• the surface treatment method is not particularly limited, and examples include physical treatments such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas and/or nitrogen gas, glow discharge treatment, and oxidation using chemicals. Examples include chemical treatments such as treatment.
• the heat-sealing layer is made of olefin resin and has a heat-sealing property of being melted by heat and fused together.
• Specific examples include films made of polyethylene such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene, and olefin resins such as polypropylene, ethylene-propylene copolymers, and polymethylpentene. Can be mentioned.
• the heat-sealing layer may be surface-treated in the same manner as the stretched polyolefin film.
• the thickness of the heat seal layer is preferably 15 ⁇ m or more and 500 ⁇ m or less, more preferably 20 ⁇ m or more and 250 ⁇ m or less, and even more preferably 30 ⁇ m or more and 100 ⁇ m or less.
• the coating layer is provided directly on the stretched polyolefin film or via a printing layer described below.
• the coating layer is located at the outermost layer when viewed from the contents, and is a layer that comes into contact with the heat seal bar during bag making.
• the coating layer is a cured coating film of a coating agent containing a composite resin (A) having a polysiloxane segment (a1) and a vinyl polymer segment (a2).
• A composite resin
• the coating layer may be provided on the entire surface of the stretched polyolefin film, or may be partially provided only on the area where the heat seal bar comes into contact when bag-making the laminate of the present invention and its periphery. .
• the polysiloxane segment (a1) is a segment obtained by condensing a silane compound having a silanol group and/or a hydrolyzable silyl group, and is represented by the following general formula (1) and/or general formula (2). and a silanol group and/or a hydrolyzable silyl group. It is preferable that the content of the polysiloxane segment (a1) is 10 to 90% by weight based on the total solid content of the composite resin (A) because it facilitates bonding with the inorganic particles (m) described below.
• a group having a bond (wherein R 4 represents a single bond or an alkylene group having 1 to 6 carbon atoms), an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an aryl group. group, an aralkyl group having 7 to 12 carbon atoms, and an epoxy group.
• the structural unit represented by the above general formula (1) and/or (2) is a three-dimensional network polysiloxane structural unit in which two or three of the silicon bonds participate in crosslinking. Although it forms a three-dimensional network structure, it does not form a dense network structure, so it does not cause gelation or the like and has good storage stability.
• the alkylene group having 1 to 6 carbon atoms in R 4 is, for example, a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a sec -Butylene group, tert-butylene group, pentylene group, isopentylene group, neopentylene group, tert-pentylene group, 1-methylbutylene group, 2-methylbutylene group, 1,2-dimethylpropylene group, 1-ethylpropylene group, hexylene group, isohexylene group, 1-methylpentylene group, 2-methylpentylene group, 3-methylpentylene group, 1,1-dimethylbutylene group, 1,2-dimethylbutylene group, 2,2-dimethylbutylene group, Examples include 1-ethylbutylene group, 1,1,2-trimethylpropylene group, 1,2,2-trimethyl
• alkyl group having 1 to 6 carbon atoms examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, and neopentyl group.
• Examples of the cycloalkyl group having 3 to 8 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group.
• Examples of the aryl group include phenyl group, naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-vinylphenyl group, and 3-isopropylphenyl group.
• Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group, diphenylmethyl group, and naphthylmethyl group.
• R 1 , R 2 and R 3 when at least one of R 1 , R 2 and R 3 is a group having a polymerizable double bond, it can be cured by active energy rays, and silanol groups and/or hydrolysis. This is preferable because the two curing mechanisms of the condensation reaction of the silyl groups increase the crosslinking density of the resulting cured product, making it possible to form a cured product with better abrasion resistance and low linear expansion.
• polysiloxane segment (a1) it is preferable that two or more groups having a polymerizable double bond exist in the polysiloxane segment (a1), more preferably 3 to 200 groups, and still more preferably 3 to 50 groups. Thereby, a molded product with lower linear expansion can be obtained.
• the coefficient of linear expansion can be designed to be lower than that of a stretched polyolefin film, and the heat resistance of the laminate can be improved. can be improved.
• the term "polymerizable double bond” is a general term for groups that can undergo a growth reaction by free radicals, among vinyl groups, vinylidene groups, and vinylene groups.
• the content of polymerizable double bonds refers to the weight percent of vinyl groups, vinylidene groups, or vinylene groups in the polysiloxane segment.
• the structure Q in the formula indicates that a plurality of vinyl groups may be bonded to the aromatic ring.
• a structure such as the following structural formula (4) may also be included.
• the polysiloxane segment (a1) when at least one of R 1 , R 2 and R 3 in the above formula is an epoxy group, it can be cured by heat curing or active energy ray curing, and the epoxy group and the silanol group Due to the two curing mechanisms of the condensation reaction of the hydrolyzable silyl group and/or the condensation reaction of the hydrolyzable silyl group, the crosslinking density of the obtained cured product is increased, and a cured product having an excellent low coefficient of linear expansion can be formed.
• a silanol group is a silicon-containing group having a hydroxyl group directly bonded to a silicon atom.
• the silanol group is preferably a silanol group formed by bonding an oxygen atom having a bond with a hydrogen atom in a structural unit represented by general formula (1) and/or (2).
• a hydrolyzable silyl group is a silicon-containing group having a hydrolyzable group directly bonded to a silicon atom, and includes, for example, a group represented by the following general formula (5).
• R 5 is a monovalent organic group such as an alkyl group, an aryl group, or an aralkyl group
• R 6 is a halogen atom, an alkoxy group, an acyloxy group, a phenoxy group, an aryloxy group, a mercapto group, an amino (b is an integer from 0 to 2.)
• alkyl group for R 5 examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group.
• Examples of the aryl group include phenyl group, naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-vinylphenyl group, and 3-isopropylphenyl group.
• Examples of the aralkyl group include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.
• Examples of the halogen atom in R 6 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
• Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, tertiary-butoxy group, and the like.
• Examples of the acyloxy group include formyloxy, acetoxy, propanoyloxy, butanoyloxy, pivaloyloxy, pentanoyloxy, phenylacetoxy, acetoacetoxy, benzoyloxy, naphthoyloxy, and the like.
• Examples of the aryloxy group include phenyloxy and naphthyloxy.
• Examples of the alkenyloxy group include vinyloxy group, allyloxy group, 1-propenyloxy group, isopropenyloxy group, 2-butenyloxy group, 3-butenyloxy group, 2-petenyloxy group, 3-methyl-3-butenyloxy group, 2 -hexenyloxy group and the like.
• the hydrolyzable silyl group represented by general formula (5) becomes a silanol group.
• methoxy group and ethoxy group are preferred because they have excellent hydrolyzability.
• the hydrolyzable silyl group is a structural unit represented by general formula (1) and/or general formula (2) in which an oxygen atom having a bond is bonded to or substituted with the hydrolyzable group.
• a hydrolyzable silyl group is preferred.
• Silanol groups and hydrolyzable silyl groups undergo a hydrolytic condensation reaction between the hydroxyl groups in the silanol groups and the hydrolyzable groups in the hydrolysable silyl groups, increasing the crosslinking density of the polysiloxane structure and increasing its resistance. It is possible to form a cured product with excellent abrasion resistance and low linear expansion.
• a polysiloxane segment (a1) containing a silanol group or a hydrolyzable silyl group to a vinyl polymer segment (a2) described below through a bond represented by the following general formula (6), use.
• the polysiloxane segment (a1) is not particularly limited except that it has a structural unit represented by the general formula (1) and/or (2), a silanol group and/or a hydrolyzable silyl group, and it does not contain any other groups. May contain.
• the vinyl polymer segment (a2) is a polymer segment obtained by polymerizing a vinyl group- or (meth)acrylic group-containing monomer, and is a vinyl polymer segment, an acrylic polymer segment, or a vinyl/acrylic copolymer segment. etc., and it is preferable to select these appropriately depending on the purpose. Since the composite resin (A) used in the present invention has a vinyl polymer segment (a2), it has excellent adhesion to a stretched polyolefin film.
• the acrylic polymer segment is obtained, for example, by polymerizing or copolymerizing a general-purpose (meth)acrylic monomer.
• the (meth)acrylic monomer is not particularly limited, and examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert- Alkyl (meth)acrylates having an alkyl group having 1 to 22 carbon atoms such as butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate; benzyl (meth)acrylate, 2-phenylethyl Aralkyl (meth)acrylates such as (meth)acrylate; Cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate;
• vinyl polymer segment examples include aromatic vinyl polymer segments, polyolefin polymers, fluoroolefin polymers, etc., and copolymers thereof may also be used.
• vinyl group-containing monomers may be polymerized, specifically ⁇ -olefins such as ethylene, propylene, 1,3-butadiene, and cyclopentylethylene; styrene, 1-ethynyl-4 - Methylbenzene, divinylbenzene, 1-ethynyl-4-methylethylbenzene, benzonitrile, acrylonitrile, ptert-butylstyrene, 4-vinylbiphenyl, 4-ethynylbenzyl alcohol, 2-ethynylnaphthalene, phenanthrene-9-ethynyl, etc.
• Vinyl compounds having an aromatic ring vinyl compounds having an aromatic ring; fluoroolefins such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, etc. can be preferably used. More preferred are styrene and p-tert-butylstyrene, which are vinyl compounds having an aromatic ring.
• vinyl/acrylic copolymer segments include those obtained by copolymerizing these (meth)acrylic monomers and vinyl group-containing monomers.
• the vinyl polymer segment (a2) can be obtained by a known method.
• a polymerization initiator such as tert-butyl peroxide, cumene hydroperoxide, or diisopropyl peroxycarbonate.
• the number average molecular weight of the vinyl polymer segment (a2) is preferably in the range of 500 to 200,000 in terms of number average molecular weight (hereinafter abbreviated as Mn). It can prevent thickening and gelation, and has excellent durability. Among these, Mn is more preferably in the range of 700 to 100,000, and even more preferably in the range of 1,000 to 50,000.
• the number average molecular weight of the vinyl polymer segment (a2) is a value measured by gel permeation chromatography (GPC) under the following conditions.
• Measuring device Gel permeation chromatograph GCP-244 (manufactured by WATERS) Column: 2 Shodex HFIP 80M (manufactured by Showa Denko K.K.) Solvent: dimethylformamide Flow rate: 0.5ml/min Temperature: 23°C Sample concentration: 0.1% Solubility: Completely dissolved Filtration: Myshori disk W-13-5 Injection volume: 0.300ml Detector: R-401 type differential refractometer (WATERS) Molecular weight calibration: Polystyrene (standard product)
• the vinyl polymer segment (a2) is added to the vinyl polymer segment (a2) in order to form a composite resin (A) bonded to the polysiloxane segment (a1) by a bond represented by the general formula (6). It has a silanol group and/or a hydrolyzable silyl group directly bonded to a carbon atom. Since these silanol groups and/or hydrolyzable silyl groups become bonds represented by general formula (6) in the composite resin (A), It is hardly present in the vinyl polymer segment (a2).
• a vinyl monomer containing a silanol group and/or a hydrolyzable silyl group directly bonded to a carbon bond may be used in combination with the vinyl group polymerizable monomer and the (meth)acrylic monomer.
• Examples of the vinyl monomer containing a silanol group and/or a hydrolyzable silyl group directly bonded to a carbon atom include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and vinyltri(2-methoxyethoxy)silane.
• the vinyl polymer segment (a2) may have various functional groups. For example, a group having a polymerizable double bond, an epoxy group, an alcoholic hydroxyl group, an acidic group, etc., can be introduced by adding a vinyl monomer having the corresponding functional group during polymerization. It is preferable that the vinyl polymer segment (a2) has an acid group because the coat layer is more easily peeled off from the stretched polyolefin film when subjected to the alkali treatment described below.
• vinyl monomer having an epoxy group examples include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, vinylcyclohexene oxide, glycidyl vinyl ether, methylglycidyl vinyl ether, or allylglycidyl Examples include ether.
• Examples of the vinyl monomer having an alcoholic hydroxyl group include (2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl monobutyl fumarate , polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, various ⁇ , ⁇ -ethylenically unsaturated carboxylic acids such as “Plaxel FM or Plaxel FA” [caprolactone addition monomer manufactured by Daicel Chemical Co., Ltd.] Examples include hydroxyalkyl esters of , or adducts of these with ⁇ -caprolactone.
• Monomers containing acidic groups include acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4-methylcyclohex-4-ene-1,2-dicarboxylic anhydride, Bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic anhydride 2-oct-1,3-diketospiro[4.4]non-7-ene, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, maleopimaric acid, tetrahydrophthalic acid Acid anhydride, methyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, methyl-norbornen-5-ene-2,3-dicarboxylic anhydride, norborne-5- Examples
• the coating agent used to form the coat layer may contain inorganic particles (m) in addition to the composite resin (A). Furthermore, the composite resin (A) and the inorganic particles (m) may be combined. The composite resin (A) and the inorganic particles (m) can be bonded via a siloxane bond through the polysiloxa segment (a1) that the composite resin (A) has. The presence of the inorganic particles (m) in the coat layer can further improve the heat resistance of the coat layer. Moreover, since the composite resin (A) and the inorganic particles (m) are bonded together, it can be expected that the coating layer will be more easily peeled off from the stretched polyolefin film when subjected to the alkali treatment described below.
• the inorganic particles (m) are not particularly limited as long as they do not impair the effects of the present invention, but when bonding with the polysiloxane segment (a1) via a siloxane bond, the inorganic particles (m) may be selected from those having a functional group capable of forming a siloxane bond. To be elected.
• the functional group capable of forming a siloxane bond may be any functional group capable of forming a siloxane bond, such as a hydroxyl group, a silanol group, or an alkoxysilyl group.
• the inorganic particle (m) itself may have a functional group capable of forming a siloxane bond, or the functional group may be introduced by modifying the inorganic particle (m).
• known and commonly used methods may be used, including methods such as treatment with a silane coupling agent and coating with a resin having a functional group capable of forming a siloxane bond.
• the inorganic particles (m) include alumina, magnesia, titania, zirconia, silica (quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine amorphous silica, etc.). It is preferred because it has excellent heat resistance. Alternatively, boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, etc. are preferable because they have excellent thermal conductivity.
• the inorganic particles (m) may be used alone or in combination.
• silica particles such as powdered silica and colloidal silica can be used.
• known silica particles such as powdered silica and colloidal silica can be used.
• commercially available powdered silica particles include Aerosil 50 and 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, and H122 manufactured by Asahi Glass Co., Ltd., and E220A manufactured by Nippon Silica Kogyo Co., Ltd. , E220, SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., and SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.
• colloidal silica includes, for example, methanol silica sol manufactured by Nissan Chemical Industries, Ltd., IPA-ST, PGM-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST- 20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc.
• silica particles may also be used; for example, the silica particles exemplified above may be surface-treated with a reactive silane coupling agent having a hydrophobic group, or modified with a compound having a (meth)acryloyl group. I can give you what I did.
• Examples of commercially available powdered silica modified with a compound having a (meth)acryloyl group include Aerosil RM50, R7200, and R711 manufactured by Nippon Aerosil Co., Ltd., and commercially available colloidal silica modified with a compound having a (meth)acryloyl group.
• Colloidal silica surface-treated with a reactive silane coupling agent having a hydrophobic group includes MIBK-ST, manufactured by Nissan Chemical Industries, Ltd., and MIBK-SD manufactured by Nissan Chemical Industries, Ltd. Examples include MEK-ST.
• the shape of the silica particles is not particularly limited, and spherical, hollow, porous, rod-like, plate-like, fibrous, or irregularly shaped particles can be used.
• a commercially available hollow silica particle Silinax manufactured by Nippon Steel Mining Co., Ltd., etc. can be used.
• titanium oxide particles not only extender pigments but also ultraviolet light-responsive photocatalysts can be used, such as anatase-type titanium oxide, rutile-type titanium oxide, brookite-type titanium oxide, etc. Furthermore, particles designed to respond to visible light by doping a different element into the crystal structure of titanium oxide can also be used.
• the element to be doped into titanium oxide anion elements such as nitrogen, sulfur, carbon, fluorine, and phosphorus, and cation elements such as chromium, iron, cobalt, and manganese are suitably used.
• a powder, a sol or a slurry dispersed in an organic solvent or water can be used.
• Examples of commercially available powdered titanium oxide particles include Aerosil P-25 manufactured by Nippon Aerosil Co., Ltd. and ATM-100 manufactured by Teika Co., Ltd. Furthermore, examples of commercially available slurry-like titanium oxide particles include TKD-701 manufactured by Teika Corporation.
• the primary particle diameter of the inorganic particles (m) is preferably in the range of 5 to 200 nm. If the diameter is 5 nm or more, the inorganic particles (m) in the dispersion will be well dispersed, and if the diameter is 200 nm or less, the strength of the cured product will be good. More preferably it is 10 nm to 100 nm. Note that the "particle size" herein is measured using a scanning electron microscope (TEM) or the like.
• the inorganic particles (m) are in a proportion of 5 to 90% by weight based on the total solid content of the composite resin (A) and inorganic particles (m) from the viewpoint of the balance between adhesion to the stretched polyolefin film and heat resistance.
• the amount can be changed as needed depending on the purpose. From the viewpoint of heat resistance, it is preferable that the blending amount of the inorganic particles (m) is 20% by mass or more based on the total solid content of the composite resin (A) and the inorganic particles (m).
• a step 1 of synthesizing a vinyl polymer segment (a2) having a silanol group and/or a hydrolyzable silyl group directly bonded to a carbon atom can be obtained by a manufacturing method characterized by having Step 2 of mixing an alkoxysilane and inorganic particles (m) and Step 3 of subjecting the alkoxysilane to a condensation reaction.
• each step may be performed separately or simultaneously. For example, it can be manufactured by the following method.
• Step 2 The silane compound containing a silanol group and/or a hydrolyzable silyl group and the inorganic particles (m) are mixed in Step 2, and the silane compound containing a silanol group and/or a hydrolyzable silyl group is condensed in Step 3 to form a polysiloxane.
• Step 3 After forming the segment (a1) and inorganic particle bonding, the vinyl polymer segment (a2) having a silanol group and/or hydrolyzable silyl group obtained in step 1 and the polysiloxane segment (a1) inorganic particles A method in which a bond is formed by hydrolyzing and condensing (m) again in step 3.
• Step 1 is a step of synthesizing a vinyl polymer segment (a2) having a silanol group and/or a hydrolyzable silyl group directly bonded to a carbon atom.
• a vinyl polymer segment (a2) having a silanol group and/or a hydrolyzable silyl group directly bonded to a carbon atom.
• a vinyl monomer containing a silanol group and/or a hydrolyzable silyl group directly bonded to a carbon bond may be used in combination with the vinyl group polymerizable monomer and the (meth)acrylic monomer.
• silane compound containing a silanol group and/or a hydrolyzable silyl group to the vinyl polymer segment (a2), the silanol group directly bonded to the carbon atom and/or hydrolyzable A polysiloxane segment precursor may be bonded to the silyl group.
• Step 2 is a step of mixing a silane compound containing a silanol group and/or a hydrolyzable silyl group and the inorganic particles (m).
• a silane compound a general-purpose silane compound containing a silanol group and/or a hydrolyzable silyl group, which will be described later, can be used.
• a silane compound having the group to be introduced is used in combination.
• a silane compound having both an aryl group and a silanol group and/or a hydrolyzable silyl group may be appropriately used in combination.
• a silane compound having both a group having a polymerizable double bond and a silanol group and/or a hydrolyzable silyl group may be used in combination.
• an epoxy group-containing silane compound having both a silanol group and/or a hydrolyzable silyl group may be used at the same time.
• a known dispersion method can be used for mixing.
• Mechanical means include, for example, a disperser, a dispersing machine with stirring blades such as a turbine blade, a paint shaker, a roll mill, a ball mill, an attritor, a sand mill, a bead mill, etc.
• a dispersing machine with stirring blades such as a turbine blade, a paint shaker, a roll mill, a ball mill, an attritor, a sand mill, a bead mill, etc.
• Dispersion by a bead mill using a dispersion media such as is preferred.
• As bead mills for example, Star Mill manufactured by Ashizawa Finetech Co., Ltd.; MSC-MILL, SC-MILL, and Atraitor MA01SC manufactured by Mitsui Mining Co., Ltd.; Nanograin Mill, Picograin Mill, Pure Grain Mill, and Mega manufactured by Asada Iron Works Co., Ltd.
• Step 3 is a step in which a silane compound containing a silanol group and/or a hydrolyzable silyl group is subjected to a condensation reaction.
• the silane compound containing a silanol group and/or a hydrolyzable silyl group is condensed to form a siloxane bond.
• the silanol group and/or hydrolyzable silyl group possessed by the aforementioned polysiloxane segment (a1) and the silanol group and/or hydrolyzable silyl group possessed by the aforementioned vinyl polymer segment (a2) are subjected to a dehydration condensation reaction. In this case, a bond represented by the general formula (6) occurs.
• the carbon atom constitutes a part of the vinyl polymer segment (a2)
• the silicon atom bonded only to the oxygen atom constitutes a part of the polysiloxane segment (a1).
• the silane compound containing a silanol group and/or a hydrolyzable silyl group and the inorganic particles (m) in a mixed state, the silane compound containing a silanol group and/or a hydrolyzable silyl group and the inorganic particle (m) can be condensed. A siloxane bond is formed between them, and the polysiloxane segment (a1) and the inorganic particle (m) are chemically bonded.
• the bonding position between the polysiloxane segment (a1) and the vinyl polymer segment (a2) is arbitrary.
• the polysiloxane segment (a1) is bonded to the side chain of the vinyl polymer segment (a2).
• examples include a composite resin having a graft structure in which a vinyl polymer segment (a2) and a polysiloxane segment (a1) are chemically bound, and a composite resin having a block structure in which a vinyl polymer segment (a2) and a polysiloxane segment (a1) are chemically bound.
• silanol group-containing and/or hydrolyzable silyl group-containing silane compound used in Steps 1 to 3 general-purpose silane compounds can be used.
• a tetrafunctional alkoxysilane compound such as tetramethoxysilane, tetraethoxysilane, or tetran-propoxysilane, or a partially hydrolyzed condensate of the tetrafunctional alkoxysilane compound may be used in combination without impairing the effects of the present invention.
• a tetrafunctional alkoxysilane compound or a partially hydrolyzed condensate thereof is used in combination, the silicon atoms of the tetrafunctional alkoxysilane compound are 20 mol% of the total silicon atoms constituting the polysiloxane segment (a1). It is preferable to use them together in a range that does not exceed .
• metal alkoxide compounds other than silicon atoms such as boron, titanium, zirconium, or aluminum, can also be used in combination without impairing the effects of the present invention.
• the metal atom contained in the metal alkoxide compound described above be used together in an amount not exceeding 25 mol % with respect to all the silicon atoms constituting the polysiloxane segment (a1).
• the silanol group-containing and/or hydrolyzable silyl group-containing silane compound used when forming the polysiloxane segment (a1) 40 mol% of monoalkyltrialkoxysilane having an alkyl group having 1 to 4 carbon atoms is contained. If it is above, the hydrolytic condensation of the polysiloxane segment (a1) will proceed easily, and the bond will become stronger, resulting in excellent heat resistance, which is preferable.
• the alkoxy group preferably has 1 to 4 carbon atoms, and more preferably the alkyl group has 1 to 2 carbon atoms.
• the monoalkyltrialkoxysilane having an alkyl group having 1 to 4 carbon atoms includes methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane.
• Examples include silane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, and butyltriethoxysilane, with methyltrimethoxysilane being preferred.
• silane compound having both a group having a polymerizable double bond and a silanol group and/or a hydrolyzable silyl group used when introducing a group having a polymerizable double bond for example, vinyltrimethoxy Silane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyltri(2-methoxyethoxy)silane, vinyltriacetoxysilane, vinyltrichlorosilane, 2-trimethoxysilylethyl vinyl ether, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropyltrichlorosilane, etc. are used in combination. Among these, vinyltrimethoxysilane and 3-(meth)acryloyloxypropylmethyldimeth
• an epoxy group-containing silane compound may be used.
• Epoxy group-containing silane compounds include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxyethoxysilane, ⁇ -glycidoxypropyltriacetoxysilane, and ⁇ -glycidoxypropyltrimethoxysilane.
• a silane compound having a group represented by formula (3) may be used.
• Specific examples of the silane compound having a group represented by formula (3) include p-styryltrimethoxysilane, p-styryltriethoxysilane, and the like.
• Step 2 part or all of the silanol group- and/or hydrolyzable silyl group-containing silane compound to be mixed with the inorganic particles (m) may be hydrolyzed and condensed.
• a dispersion medium may be used for the purpose of adjusting the solid content and viscosity.
• the dispersion medium may be any liquid medium that does not impair the effects of the present invention, and includes various organic solvents, water, liquid organic polymers, and monomers.
• organic solvents examples include ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); cyclic ethers such as tetrahydrofuran (THF) and dioxolane; esters such as methyl acetate, ethyl acetate, and butyl acetate; Examples include aromatics such as toluene and xylene, and alcohols such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether, and normal propyl alcohol, and these can be used alone or in combination.
• ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK)
• cyclic ethers such as tetrahydrofuran (THF) and dioxolane
• esters such as methyl acetate, e
• the coating agent used in the present invention may contain, in addition to the composite resin (A), a polymer or monomer having a reactive group that directly contributes to the curing reaction with the composite resin (A).
• the vinyl polymer segment (a2) in the composite resin (A) has an alcoholic hydroxyl group.
• the polyisocyanate is preferably contained in an amount of 5 to 50% by weight based on the total amount of the composite resin (A).
• urethane bonds which are soft segments, are formed and work to relieve stress concentration due to hardening derived from polymerizable double bonds.
• polyisocyanate There are no particular limitations on the polyisocyanate used, and known polyisocyanates can be used.
• the isocyanate group in the polyisocyanate is preferably 3 to 30% by weight from the viewpoint of conformability of the coating layer. If the content of isocyanate groups in the polyisocyanate exceeds 30%, there is a possibility that the effect of improving followability due to stress relaxation will not be expressed.
• the reaction between the polyisocyanate and the hydroxyl group in the system (this is the hydroxyl group in the vinyl polymer segment (a2) or the hydroxyl group in the active energy ray-curable monomer having an alcoholic hydroxyl group, which will be described later) can be carried out by heating, etc. is not necessary, and the reaction will occur gradually if left at room temperature. Further, if necessary, the reaction between the alcoholic hydroxyl group and the isocyanate may be promoted by heating at 80° C. for several minutes to several hours (20 minutes to 4 hours). In that case, a known urethanization catalyst may be used if necessary. The urethanization catalyst is appropriately selected depending on the desired reaction temperature.
• an active energy ray-curable monomer when using an active energy ray-curable monomer as a reactive compound, it is preferable to contain a polyfunctional vinyl monomer characterized by having a plurality of vinyl reactive groups.
• the polyfunctional vinyl monomer is not particularly limited, and known monomers such as polyfunctional vinyl monomers and polyfunctional (meth)acrylic monomers can be used.
• Examples include polyfunctional (meth)acrylates having two or more polymerizable double bonds in one molecule, such as (erythritol) pentaacrylate and di(pentaerythritol) hexaacrylate.
• acrylates having hydroxyl groups such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate are preferred.
• polyvalent (meth)acrylates having an isocyanurate structure specifically, tris(2-acryloyloxyethyl)isocyanurate, ⁇ -caprolactone-modified tris(2-acryloyloxyethyl)isocyanurate, -acryloyloxyethyl) isocyanurate, isocyanuric acid EO-modified diacrylate, and the like.
• a monofunctional vinyl monomer can also be used in combination as a reactive compound.
• hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, caprolactone-modified hydroxy (meth)acrylate for example, "Plaxel” manufactured by Daicel Chemical Industries, Ltd.
• phthalic acid for example, "Plaxel” manufactured by Daicel Chemical Industries, Ltd.
• the glass transition temperature of the reactive compound is a value obtained by converting the temperature (K) calculated using the following Fox formula into a Celsius temperature (° C.).
• W1, W2, W3, and W4 mean mass fractions (mass %) of various components.
• Tg1, Tg2, Tg3, and Tg4 mean the glass transition temperature (K) of homopolymers of various components.
• known curing agents for epoxy resins can be used, such as phenol novolac resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol Addition resin, phenol aralkyl resin (Zyrock resin), naphthol aralkyl resin, trimethylolmethane resin, tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyhydric phenol compound with phenol nucleus linked by bismethylene group), biphenyl-modified naphthol resin (polyhydric naphthol compound with phenol nucleus linked by bismethylene group), aminotriazine-modified phenol resin (phenol nucleus with melamine, benzoguanamine, etc.) Phenolic compounds
• a polymer or monomer that can introduce acidic groups into the coating layer as the reactive compound. This can be expected to have the effect of making it easier for the coat layer to peel off from the stretched polyolefin film when subjected to the alkali treatment described below.
• reaction products include acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4-methylcyclohex-4-ene-1,2-dicarboxylic anhydride, Bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic anhydride 2-oct-1,3-diketospiro[4.4]non-7-ene, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, maleopimaric acid, tetrahydrophthalic acid Acid anhydride, methyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, methyl-norbornen-5-ene-2,3-dicarboxylic anhydride, norborne-5- Examples include ene-2
• a polymer or monomer that can introduce an ether skeleton into the coating layer as the reactive compound. This can be expected to have the effect of making it easier for the coat layer to peel off from the stretched polyolefin film when subjected to the alkali treatment described below.
• the average number of functional groups of the reactive compound can be adjusted as appropriate, but it is preferably 2 to 6.
• the coefficient of linear expansion of the coating layer can be designed to be low, and the heat resistance of the laminate can be improved.
• the amount used is preferably 1 to 85% by weight, more preferably 5 to 80% by weight of the total solid content of the coating agent containing the composite resin (A).
• a curing accelerator can also be used in combination as necessary.
• Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazole, organic acid metal salts, Lewis acids, and amine complex salts.
• imidazole compounds include 2-ethyl-4-methylimidazole
• phosphorus compounds include triphenylphosphine
• tertiary amines include 1,8-diazabicyclo. -[5.4.0]-undecene (DBU) is preferred.
• a dispersion medium may be used to adjust the solid content and viscosity of the coating agent used in the present invention.
• the dispersion medium may be any liquid medium that does not impair the effects of the present invention, and includes various aqueous solvents, organic solvents, liquid organic polymers, and the like.
• organic solvents examples include ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); cyclic ethers such as tetrahydrofuran (THF) and dioxolane; esters such as methyl acetate, ethyl acetate, and butyl acetate; Examples include aromatics such as toluene and xylene, alcohols such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether, and normal propyl alcohol, and these can be used alone or in combination, but among them Methyl ethyl ketone is preferred from the viewpoint of volatility during coating and solvent recovery.
• ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK)
• cyclic ethers such as tetrahydr
• the liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction, and includes, for example, carboxyl group-containing polymer modified products (Floren G-900, NC-500: Kyoeisha), acrylic polymers (Floren WK-20: Kyoeisha), Examples include amine salts of specially modified phosphoric acid esters (HIPLAAD ED-251: Kusumoto Kasei), modified acrylic block copolymers (DISPERBYK2000; BYK Chemie), and the like.
• carboxyl group-containing polymer modified products Floren G-900, NC-500: Kyoeisha
• acrylic polymers Floren WK-20: Kyoeisha
• Examples include amine salts of specially modified phosphoric acid esters (HIPLAAD ED-251: Kusumoto Kasei), modified acrylic block copolymers (DISPERBYK2000; BYK Chemie), and the like.
• Coating agents include catalysts, polymerization initiators, organic fillers, inorganic fillers, organic solvents, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow regulators, dyes, leveling agents, It may also contain rheology control agents, ultraviolet absorbers, antioxidants, plasticizers, and the like.
• the coating layer is provided by applying the above-mentioned coating agent onto the stretched polyolefin film directly or via a printed layer and drying it. It is more preferable to use a reactive functional group of the composite resin (A) or the inorganic particles (m) for curing.
• the curing method is appropriately selected depending on the reactive functional groups possessed by the composite resin (A) and the inorganic particles (m).
• the method for applying the coating agent is not particularly limited, and conventionally known methods can be used. Examples include spray coating, direct gravure coating, gravure kiss reverse coating, offset guaviar coating, flexo coating, offset coating, bar coating, roll kiss coating, forward rotation roll coating, reverse roll coating, slot die coating, vacuum die coating, (micro ) Various coating methods include chamber doctor coat, air doctor coat, blade coat, knife coat, spin coat, and dipping coat.
• the thickness of the coating layer can be adjusted as appropriate, but from the viewpoint of heat resistance, it is preferably 0.3 ⁇ m or more. From the viewpoint of adhesion, the thickness is preferably 6 ⁇ m or less.
• the coating agent used in the present invention can be thermally cured, for example, via the silanol group and/or hydrolyzable silyl group that the polysiloxane segment (a1) of the composite resin (A) has.
• thermosetting it is possible to heat and cure the material alone, but it is also possible to use a curing catalyst in combination.
• curing catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate, and acetic acid; inorganic bases such as sodium hydroxide or potassium hydroxide; tetraisopropyl titanate, tetra Titanate esters such as butyl titanate; 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4 - Compounds containing various basic nitrogen atoms such as diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine, dimethylbenzylamine, monoethanolamine, imidazole, 1-methylimidazole; tetramethyl Various quaternary ammonium salts such as ammonium salt, tetrabutylammonium salt,
• the catalysts may be used alone or in combination of two or more.
• the urethanization reaction can be caused by adding a catalyst.
• the vinyl polymer segment (a2) or the polysiloxane segment (a1) has a group having a polymerizable double bond
• the reaction can be carried out by using a thermal polymerization initiator.
• the vinyl polymer segment (a2) or the polysiloxane segment (a1) has an epoxy group, by blending a compound having an epoxy group, a hydroxyl group, a carboxyl group, an acid anhydride, or an amide group, A general-purpose curing agent for epoxy resins can be used.
• thermosetting resin examples include vinyl resins, unsaturated polyester resins, polyurethane resins, epoxy resins, epoxy ester resins, acrylic resins, phenol resins, petroleum resins, ketone resins, silicone resins, and modified resins thereof.
• the vinyl polymer segment (a2) or the polysiloxane segment (a1) when the vinyl polymer segment (a2) or the polysiloxane segment (a1) has a polymerizable unsaturated group, it can also be cured by active energy ray curing. More specifically, photocuring is possible by adding a photopolymerization initiator to the coating agent. As photocuring, ultraviolet curing is preferred. Any known photopolymerization initiator may be used, and for example, one or more selected from the group consisting of acetophenones, benzyl ketals, and benzophenones can be preferably used.
• acetophenones include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4- Examples include (2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone.
• benzyl ketals include 1-hydroxycyclohexyl-phenyl ketone and benzyl dimethyl ketal.
• benzophenones include benzophenone and methyl o-benzoylbenzoate.
• benzoins include benzoin, benzoin methyl ether, benzoin isopropyl ether, and the like.
• the photopolymerization initiators may be used alone or in combination of two or more.
• polyfunctional (meth)acrylate When curing with ultraviolet rays, polyfunctional (meth)acrylate may be added if necessary, and the cured density will be improved, thereby improving heat resistance. Furthermore, monofunctional (meth)acrylate may be used.
• a low pressure mercury lamp for example, a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, an argon laser, a helium/cadmium laser, an ultraviolet light emitting diode, etc. can be used.
• the coating layer can be formed by curing with an electron beam using an electron beam in which electrons are artificially accelerated in an accelerator as the active energy ray.
• the coating agent does not contain a photopolymerization initiator.
• the energy intensity of the electron beam used for electron beam curing is 30,000 to 300,000 eV, and the irradiation dose is 5 to 100 kGy ⁇ m/min. (kilogray) is preferable.
• the coating layer is preferably provided by curing the above-mentioned coating agent by active energy ray curing, and more preferably by curing by electron beam curing.
• electron beam curing since the coating layer does not contain a photopolymerization initiator, it is possible to obtain a laminate that is odorless or has suppressed odor, and photopolymerization does not start when the laminate of the present invention is used as a food packaging material. There is no concern that the agent will transfer to the contents.
• the effect of heat on the irradiated object is small, so there is almost no distortion, wrinkles, deformation, etc. due to heat, and processing can be performed at line speeds of 10 to 400 m/min or higher. be.
• the stretched polyolefin film and the heat seal layer can be bonded together by any method, but for example, they can be bonded together using a two-component curing adhesive containing a polyol composition and a polyisocyanate composition.
• the cured coating film of the two-part curable adhesive is referred to as an adhesive layer.
• the polyol composition contains a polyol having multiple hydroxyl groups.
• Such polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3propanediol, 1,4-butanediol, 1,5-pentanediol, 3- Methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxy Glycols such as benzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol;
• trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol
• Bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol F
• dimer diol A polyether polyol obtained by addition-polymerizing an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, or cyclohexylene in the presence of a polymerization initiator such as the glycol, trifunctional or tetrafunctional aliphatic alcohol, etc.
• a polyether urethane polyol obtained by further increasing the molecular weight of a polyether polyol with the aromatic or aliphatic polyisocyanate;
• Polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as propiolactone, butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone, and the aforementioned glycols, glycerin, trimethylolpropane, pentaerythritol, etc.
• a polyester polyol (1) which is a reaction product with a polyhydric alcohol
• Polyester polyol (2) obtained by reacting a bifunctional polyol such as the glycol, dimer diol, or bisphenol with a polyhydric carboxylic acid
• Polyester polyol (3) obtained by reacting a trifunctional or tetrafunctional aliphatic alcohol with a polycarboxylic acid
• a polyester polyol (4) obtained by reacting a bifunctional polyol, the trifunctional or tetrafunctional aliphatic alcohol, and a polyhydric carboxylic acid
• Polyester polyol (5) which is a polymer of hydroxyl acids such as dimethylolpropionic acid and castor oil fatty acid;
• polyhydric carboxylic acids used in the preparation of polyester polyols (2) to (4) include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3- Aliphatic dicarboxylic acids such as cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid acid, aromatic dicarboxylic acids such as naphthalic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid; and anhydrides or ester-forming derivatives of these aliphatic or dicarboxylic acids; p -hydroxybenzo
• the polyol contains at least one of a polyether polyol or a polyester polyol.
• the number average molecular weight of the polyol is not particularly limited, but is preferably 300 or more and 4000 or less, as an example. Note that the number average molecular weight in this specification is a value measured by gel permeation chromatography (GPC) under the following conditions.
• Measuring device HLC-8320GPC manufactured by Tosoh Corporation Column: Tosoh Corporation TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL Detector: RI (differential refractometer)
• Data processing Multi-station GPC-8020model II manufactured by Tosoh Corporation Measurement conditions: Column temperature 40°C Solvent: Tetrahydrofuran Flow rate: 0.35 ml/min Standard: Monodisperse polystyrene Sample: 0.2% by mass (calculated as resin solids) of tetrahydrofuran solution filtered through a microfilter (100 ⁇ l)
• the polyisocyanate composition includes a polyisocyanate compound having multiple isocyanate groups.
• the polyisocyanate compound conventionally known ones can be used without particular limitation, including aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and buret, nurate, and adduct forms of these diisocyanates. Examples include allophanate compounds, carbodiimide modified products, uretdione modified products, and urethane prepolymers obtained by reacting these polyisocyanates with polyols, and these can be used alone or in combination.
• aromatic diisocyanates examples include 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, and polymethylene polyphenyl polyisocyanate (also referred to as polymeric MDI or crude MDI).
• Aroaliphatic diisocyanate means an aliphatic isocyanate having one or more aromatic rings in the molecule, and includes m- or p-xylylene diisocyanate (also known as XDI), ⁇ , ⁇ , ⁇ ', ⁇ '-tetra Examples include, but are not limited to, methyl xylylene diisocyanate (also known as TMXDI).
• aliphatic diisocyanates examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and dodecamethylene. Examples include, but are not limited to, diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.
• alicyclic diisocyanates examples include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, isophorone diisocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, and 1,4-cyclohexane.
• IPDI isophorone diisocyanate
• 1,3-cyclopentane diisocyanate 1,3-cyclohexane diisocyanate
• 1,4-cyclohexane examples include diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, etc. but not limited to.
• the same polyols as those exemplified above can be used. It is preferable to use at least one of polyalkylene glycol or polyester polyol.
• polyisocyanates obtained by reacting aromatic polyisocyanates with polyalkylene glycols having number average molecular weights in the range of 200 to 6,000, and aromatic polyisocyanates and polyalkylene glycols having number average molecular weights in the range of 200 to 3,000.
• a polyisocyanate obtained by reacting with a polyester polyol in the following range is preferable because it can impart appropriate flexibility to the cured product. It is preferable that the isocyanate content determined by titration (using di-n-butylamine) is 5 to 20% by mass, since the resin has an appropriate viscosity and excellent coating properties.
• polyisocyanates obtained by reacting aromatic polyisocyanates with polyester polyols having a number average molecular weight of 200 to 3,000 are used.
• a polyisocyanate obtained by reacting a polyester polyol having a number average molecular weight in the range of 200 to 6,000 with a mixture of polyalkylene glycol having a number average molecular weight in the range of 200 to 6,000 is preferable because it has excellent adhesive strength.
• a resin having an isocyanate content of 5 to 20% by mass according to a conventional method (using di-n-butylamine) is preferable because it provides an appropriate resin viscosity and excellent coating properties.
• the polyisocyanate compound is a urethane prepolymer
• the polyisocyanate and polyol used in the synthesis reaction have an equivalent ratio [NCO]/[OH] of isocyanate groups to hydroxyl groups in the range of 1.5 to 5.0. It is preferable that the viscosity of the adhesive falls within an appropriate range, resulting in good coating properties.
• the adhesive may contain components other than those mentioned above.
• Other components may be included in either or both of the polyol composition and the polyisocyanate composition, or they may be prepared separately from the polyol composition and the polyisocyanate composition and added to the polyol composition and the polyisocyanate composition immediately before applying the adhesive. It may be used by mixing with other substances. Each component will be explained below.
• the adhesive used in the present invention may contain a catalyst.
• the catalyst include metal catalysts, amine catalysts, aliphatic cyclic amide compounds, and the like.
• metal-based catalysts include metal complex-based, inorganic metal-based, and organic metal-based catalysts.
• Metal complex catalysts include a group consisting of Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum), and Co (cobalt).
• acetylacetonate salts of metals selected from among these include iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, and zirconia acetylacetonate.
• Examples of the inorganic metal catalyst include those selected from Sn, Fe, Mn, Cu, Zr, Th, Ti, Al, Co, and the like.
• organometallic catalysts include organic zinc compounds such as zinc octylate, zinc neodecanoate, and zinc naphthenate; stannath diacetate, stannath dioctoate, stannath dioleate, stannath dilaurate, dibutyltin diacetate, and dibutyltin dilaurate.
• organic tin compounds such as dioctyltin dilaurate, dibutyltin oxide, and dibutyltin dichloride
• organic nickel compounds such as nickel octylate and nickel naphthenate
• organic cobalt compounds such as cobalt octylate and cobalt naphthenate, bismuth octylate, and neodecanoic acid.
• At least one of organic bismuth compounds such as bismuth and bismuth naphthenate, tetraisopropyloxytitanate, dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, aliphatic diketones, aromatic diketones, and alcohols having 2 to 10 carbon atoms.
• organic bismuth compounds such as bismuth and bismuth naphthenate, tetraisopropyloxytitanate, dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, aliphatic diketones, aromatic diketones, and alcohols having 2 to 10 carbon atoms.
• examples include titanium-based compounds such as titanium chelate complexes used as ligands.
• amine catalysts include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, 2-methylquinuclidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl Propylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N', N",N"-pentamethyldipropylenetriamine, N,N,N',N'-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl)ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol , N,N-dimethyl-N'-(2-hydroxyethyl)ethylenediamine, N,N-dimethyl-N'-(2-
• Examples of the aliphatic cyclic amide compound include ⁇ -valerolactam, ⁇ -caprolactam, ⁇ -enanthollactam, ⁇ -capryllactam, ⁇ -propiolactam, and the like. Among these, ⁇ -caprolactam is more effective in accelerating curing.
• the adhesive used in the present invention may contain an acid anhydride.
• the acid anhydride include cyclic aliphatic acid anhydrides, aromatic acid anhydrides, unsaturated carboxylic acid anhydrides, etc., and one type or a combination of two or more types can be used.
• phthalic anhydride trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, dodecenylsuccinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic acid
• poly(ethyl octadecanedioic acid) anhydride poly(phenylhexadecanedioic acid) anhydride
• tetrahydrophthalic anhydride methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride , methylhimic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexenedicarboxylic anhydride, methylcyclohexenetetracarboxylic anhydride, ethylene glycol bistrimelitate dianhydride, Het's acid
• glycols that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol, and neopentyl glycol; polyether glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Furthermore, a copolymerized polyether glycol of two or more types of glycols and/or polyether glycols can also be used.
• the adhesive used in the present invention may contain a coupling agent.
• the coupling agent include a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent.
• silane coupling agent examples include ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl)- ⁇ -amino Aminosilanes such as propyltrimethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane; ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxy Epoxysilanes such as propyltriethoxysilane; vinylsilanes such as vinyltris( ⁇ -methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, ⁇ -methacryloxy
• titanate coupling agents include tetraisopropoxy titanium, tetra-n-butoxy titanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, and tetrastearoxy titanate.
• examples include titanium.
• aluminum-based coupling agents examples include acetalkoxyaluminum diisopropylate.
• the adhesive used in the present invention may contain a pigment.
• a pigment There are no particular restrictions on the pigments; extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, Examples include organic pigments and inorganic pigments such as metal powder pigments, luminescent pigments, and pearlescent pigments, as well as plastic pigments.
• extender pigments examples include precipitated barium sulfate, powder, precipitated calcium carbonate, calcium bicarbonate, agarite, alumina white, silica, hydrated fine powder silica (white carbon), ultrafine anhydrous silica (Aerosil), and silica sand (silica). sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, loess, etc.
• organic pigments include various insoluble azo pigments such as Benzidine Yellow, Hansa Yellow, and Laked 4R; soluble azo pigments such as Laked C, Carmine 6B, and Bordeaux 10; various types (copper) such as phthalocyanine blue and phthalocyanine green; Phthalocyanine pigments; various chlorine dyeing lakes such as rhodamine lake and methyl violet lake; various mordant dye pigments such as quinoline lake and fast sky blue; various types of anthraquinone pigments, thioindigo pigments, perinone pigments, etc.
• insoluble azo pigments such as Benzidine Yellow, Hansa Yellow, and Laked 4R
• soluble azo pigments such as Laked C, Carmine 6B, and Bordeaux 10
• various types (copper) such as phthalocyanine blue and phthalocyanine green
• Phthalocyanine pigments various chlorine dyeing lakes such as rhodamine lake and methyl violet lake
• various mordant dye pigments such as
• vat dye pigments examples include vat dye pigments; various quinacridone pigments such as Cyncasia Red B; various dioxazine pigments such as dioxazine violet; various condensed azo pigments such as chromophthal; and aniline black.
• Inorganic pigments include various chromates such as yellow lead, zinc chromate, molybdate orange, etc.; various ferrocyanic compounds such as navy blue; titanium oxide, zinc white, mapico yellow, iron oxide, red iron oxide, chrome oxide green, Various metal oxides such as zirconium oxide; Various sulfides or selenides such as cadmium yellow, cadmium red, and mercury sulfide; Various sulfates such as barium sulfate and lead sulfate; Various silicates such as calcium silicate and ultramarine blue.
• Acid salts Various carbonates such as calcium carbonate and magnesium carbonate; Various phosphates such as cobalt violet and manganese violet; Various metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, bronze powder, and brass powder; Examples include flake pigments of these metals, mica flake pigments; mica flake pigments coated with metal oxides, metallic pigments such as mica-like iron oxide pigments, pearl pigments; graphite, carbon black, and the like.
• plastic pigment examples include "Grandeur PP-1000” and “PP-2000S” manufactured by DIC Corporation.
• the pigment to be used may be appropriately selected depending on the purpose, but for example, it is preferable to use inorganic oxides such as titanium oxide and zinc white as white pigments because of their excellent durability, weather resistance, and design. It is preferable to use carbon black as the pigment.
• the adhesive used in the present invention may contain a plasticizer.
• plasticizers include phthalic acid plasticizers, fatty acid plasticizers, aromatic polycarboxylic acid plasticizers, phosphoric acid plasticizers, polyol plasticizers, epoxy plasticizers, polyester plasticizers, and carbonate plasticizers. Examples include plasticizers.
• phthalic acid plasticizers examples include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, diheptyl phthalate, di-(2-ethylhexyl) phthalate, di-n-octyl phthalate, and dinonyl.
• fatty acid plasticizers include adipic acids such as di-n-butyl adipate, di-(2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate, di(C6-C10 alkyl) adipate, and dibutyl diglycol adipate.
• azelaic acid plasticizers such as di-n-hexyl azelate, di-(2-ethylhexyl) azelate, diisooctyl azelate, e.g.
• di-n-butyl sebacate di-(2- Sebacic acid plasticizers such as ethylhexyl) sebacate and diisononyl sebacate
• maleic acid plasticizers such as dimethyl maleate, diethyl maleate, di-n-butyl maleate, and di-(2-ethylhexyl) maleate, e.g.
• di-n-butyl fumarate, di-(2-ethylhexyl) fumarate, and other fumaric acid plasticizers such as monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, Itaconic acid plasticizers such as di-(2-ethylhexyl) itaconate, for example, stearic acid plasticizers such as n-butyl stearate, glycerin monostearate, diethylene glycol distearate, for example butyl oleate, glyceryl monooleate, Oleic acid plasticizers such as diethylene glycol monooleate; citric acids such as triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, acetyl tri-(2-ethylhe
• aromatic polycarboxylic acid plasticizers include tri-n-hexyl trimellitate, tri-(2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisooctyl trimellitate, and triisononyl.
• Trimellitic acid plasticizers such as trimellitate, tridecyl trimellitate, and triisodecyl trimellitate; for example, pyromellitic acid plasticizers such as tetra-(2-ethylhexyl)pyromellitate and tetra-n-octylpyromellitate. Examples include plasticizers.
• Examples of phosphoric acid plasticizers include triethyl phosphate, tributyl phosphate, tri-(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, cresyl phenyl phosphate, and tricresyl phosphate.
• Examples include dilyphosphate, tricylenylphosphate, tris(chloroethyl)phosphate, tris(chloropropyl)phosphate, tris(dichloropropyl)phosphate, tris(isopropylphenyl)phosphate, and the like.
• polyol plasticizers examples include diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di-(2-ethyl butyrate), and triethylene glycol di-(2-ethylhexoate).
• glycol-based plasticizers such as dibutylmethylene bisthioglycolate
• glycerin-based plasticizers such as glycerol monoacetate, glycerol triacetate, and glycerol tributyrate.
• epoxy plasticizers include epoxidized soybean oil, epoxybutyl stearate, di2-ethylhexyl epoxyhexahydrophthalate, diisodecyl epoxyhexahydrophthalate, epoxy triglyceride, epoxidized octyl oleate, and epoxidized decyl oleate. Examples include.
• polyester plasticizer examples include adipic acid polyester, sebacic acid polyester, and phthalic acid polyester.
• carbonate plasticizers examples include propylene carbonate and ethylene carbonate.
• plasticizer examples include partially hydrogenated terphenyl, adhesive plasticizers, and polymerizable plasticizers such as diallyl phthalate, acrylic monomers, and oligomers. These plasticizers can be used alone or in combination of two or more.
• the adhesive used in the present invention may contain a phosphoric acid compound.
• Phosphoric acid compounds include phosphoric acid, pyrophosphoric acid, triphosphoric acid, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, isododecyl acid phosphate, butoxy Examples include ethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, and polyoxyethylene alkyl ether phosphate.
• the adhesive used in the present invention may be in either a solvent-based or solvent-free form.
• a "solvent type" adhesive refers to an adhesive that is applied to a base material, heated in an oven, etc. to volatilize the organic solvent in the coating film, and then bonded to another base material. This refers to the form used in the so-called dry lamination method.
• Either or both of the polyol composition and the polyisocyanate composition contain an organic solvent capable of dissolving (diluting) the constituent components of the polyol composition and the polyisocyanate composition.
• organic solvents examples include esters such as ethyl acetate, butyl acetate, and cellosolve acetate, ketones such as acetone, methyl ethyl ketone, isobutyl ketone, and cyclohexanone, ethers such as tetrahydrofuran and dioxane, and aromatic hydrocarbons such as toluene and xylene. , halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethyl sulfoxide, dimethyl sulfamide, and the like.
• the organic solvent used as a reaction medium during the production of the constituent components of the polyol composition and polyisocyanate composition may also be used as a diluent during coating.
• a "solvent-free" adhesive means that the polyol composition and polyisocyanate composition do not substantially contain highly soluble organic solvents such as those exemplified above, especially ethyl acetate or methyl ethyl ketone.
• non-solvent laminating method which is a method in which an adhesive is applied to a base material and then bonded to another base material without going through the process of heating in an oven or the like to volatilize the solvent.
• the constituent components of polyol compositions and polyisocyanate compositions and the organic solvents used as reaction media during the production of their raw materials cannot be completely removed, and trace amounts of organic solvents remain in polyol compositions and polyisocyanate compositions. If it is stored, it is considered to be substantially free of organic solvents. Further, when the polyol composition contains a low molecular weight alcohol, the low molecular weight alcohol reacts with the polyisocyanate composition and becomes a part of the coating film, so there is no need to volatilize it after coating. Therefore, such forms are also treated as solvent-free adhesives, and low molecular weight alcohols are not considered organic solvents.
• the adhesive has a ratio [NCO]/[OH] of the number of moles of isocyanate groups contained in the polyisocyanate composition [NCO] to the number of moles of hydroxyl groups contained in the polyol composition [OH] of 1.0 to 3. It is preferable to mix and use it so that it becomes 0. Thereby, appropriate curability can be obtained without depending on the environmental humidity at the time of coating.
• the thickness of the adhesive layer can be adjusted as appropriate, and is, for example, 0.5 ⁇ m or more and 6 ⁇ m or less.
• the heat-sealing layer may further include a vapor-deposited layer on the surface facing the stretched polyolefin film.
• the deposited layer include a deposited layer containing a metal such as aluminum or an inorganic oxide such as aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, or barium oxide. From the viewpoint of oxygen barrier properties and water vapor barrier properties, an aluminum vapor deposited layer is preferred.
• the stretched polyolefin film has a vapor-deposited layer containing an inorganic oxide such as aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, barium oxide, etc. on the heat-sealing layer side. may be provided.
• an inorganic oxide such as aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, barium oxide, etc.
• vapor deposition layer As a method for forming the vapor deposition layer, conventionally known methods can be employed, such as vacuum vapor deposition, physical vapor deposition (PVD) such as sputtering and ion plating, and plasma chemical vapor deposition. Examples include chemical vapor deposition methods (CVD methods) such as chemical vapor deposition methods, thermal chemical vapor deposition methods, and photochemical vapor deposition methods.
• the thickness of the vapor deposited film is preferably 1 nm or more and 100 nm or less, more preferably 15 nm or more and 60 nm or less, and even more preferably 10 nm or more and 40 nm or less.
• the thickness is preferably 1 nm or more and 140 nm or less, more preferably 5 nm or more and 30 nm or less, and even more preferably 5 nm or more and 20 nm or less.
• a composite film consisting of two or more layers of vapor-deposited films of different types of inorganic oxides can be formed and used by using both physical vapor deposition and chemical vapor deposition.
• the degree of vacuum in the deposition chamber is preferably about 10 -2 to 10 -8 mbar before introducing oxygen, and preferably about 10 -1 to 10 -6 mbar after introducing oxygen.
• the amount of oxygen introduced varies depending on the size of the vapor deposition machine and other factors.
• an inert gas such as argon gas, helium gas, nitrogen gas, etc. may be used as a carrier gas within a range that does not cause any problem.
• the transport speed of the film is preferably about 10 to 800 m/min, particularly about 50 to 600 m/min.
• the laminate of the present invention may have a barrier coat layer at any position closer to the heat seal layer than the above-mentioned coat layer.
• the laminate of the present invention has a vapor deposited layer, it is preferably provided on the vapor deposited layer. This can suppress the occurrence of cracks or the like in the vapor deposited layer, and the laminate of the present invention can have excellent gas barrier properties.
• the barrier coat layer can be provided by a conventionally known method using a conventionally known composition.
• a gas barrier property of an alkoxide hydrolyzate or an alkoxide hydrolysis condensate obtained by polycondensing an alkoxide and a water-soluble polymer by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent It is a film made of a composition. It may further contain a silane coupling agent.
• R 1 n M(OR 2 ) m At least one kind of alkoxide represented by the general formula R 1 n M(OR 2 ) m can be used.
• R 1 and R 2 represent an organic group having 1 to 8 carbon atoms
• M represents a metal atom
• n represents an integer of 0 or more
• m represents an integer of 1 or more
• n+m represents the valence of M. represents.
• the metal atom M silicon, zirconium, titanium, aluminum, etc.
• Specific examples of the organic group represented by R 1 and R 2 include alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, and i-butyl group.
• alkyl groups may be the same or different in the same molecule.
• alkoxides include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.
• polyvinyl alcohol resin As the water-soluble polymer, polyvinyl alcohol resin, ethylene-vinyl alcohol copolymer, or both can preferably be used.
• Commercially available resins may be used as these resins, such as Eval EP-F101 (ethylene content: 32 mol%) manufactured by Kuraray Co., Ltd. and Soarnol manufactured by Nippon Gosei Chemical Industry Co., Ltd. as ethylene/vinyl alcohol copolymers. D2908 (ethylene content: 29 mol%) and the like can be used.
• polyvinyl alcohol RS-110 manufactured by Kuraray Co., Ltd.
• the content of the water-soluble polymer is, for example, 5 to 500 parts by mass per 100 parts by mass of the alkoxide.
• a tertiary amine is used as the sol-gel method catalyst.
• N,N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, etc. can be used.
• Particularly preferred is N,N-dimethylbenzylamine.
• organic solvent methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol, etc. can be used.
• silane coupling agent examples include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, and (3-(3,4-epoxycyclohexyl)ethyltrimethoxysilane).
• the amount of the silane coupling agent used is 1 to 20 parts by weight per 100 parts by weight of the alkoxide.
• the barrier coat layer is formed by applying one or more times by a conventionally known method such as roll coating using a gravure roll coater, spray coating, spin coating, dipping, brush coating, bar coating, or applicator.
• the thickness of the barrier coat layer is adjusted as appropriate, and is, for example, approximately 0.01 to 100 ⁇ m, more preferably 0.01 to 50 ⁇ m.
• the laminate of the present invention may have a printed layer.
• the printing layer is a layer on which characters, figures, symbols, and other desired patterns are printed using liquid ink.
• the printing layer can be provided at any position, but for example, between the stretched polyolefin base material and the adhesive layer (if a vapor deposition layer or gas barrier coat layer is provided, between these layers and the adhesive layer), or the stretched An example is between the polyolefin base material and the coating layer.
• liquid ink is a general term for solvent-based inks used in gravure printing or flexographic printing.
• the ink may contain a resin, a colorant, and a solvent as essential components, or it may be a so-called clear ink that contains a resin and a solvent but does not substantially contain a colorant.
• the resin used in the liquid ink is not particularly limited, and examples include acrylic resin, polyester resin, styrene resin, styrene-maleic acid resin, maleic acid resin, polyamide resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, Vinyl chloride-acrylic copolymer resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, polyvinyl chloride resin, chlorinated polypropylene resin, cellulose resin, epoxy resin, alkyd resin, rosin resin, rosin-modified maleic acid resin , ketone resin, cyclized rubber, chlorinated rubber, butyral, petroleum resin, etc., and one type or two or more types can be used in combination.
• at least one type, or two or more types selected from polyurethane resins, vinyl chloride-vinyl acetate copolymer resins, and cellulose resins are used.
• Coloring agents used in liquid ink include inorganic pigments such as titanium oxide, Bengara, antimony red, cadmium red, cadmium yellow, cobalt blue, navy blue, ultramarine, carbon black, and graphite, soluble azo pigments, insoluble azo pigments, and azo lake.
• examples include organic pigments such as pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments, and extender pigments such as calcium carbonate, kaolin clay, barium sulfate, aluminum hydroxide, and talc.
• the organic solvent used in the liquid ink preferably does not contain aromatic hydrocarbon organic solvents. More specifically, alcohol organic solvents such as methanol, ethanol, n-propanol, isopropanol, butanol, ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, etc.
• alcohol organic solvents such as methanol, ethanol, n-propanol, isopropanol, butanol
• ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, etc.
• ester organic solvents such as n-hexane, n-heptane, and n-octane
• aliphatic hydrocarbon organic solvents such as n-hexane, n-heptane, and n-octane
• alicyclic hydrocarbon organic solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, and cyclooctane.
• the laminate of the present invention may further include a primer layer between the stretched polyolefin film and the coat layer to improve the adhesion of the coat layer.
• the heat resistance of the laminate can be improved by arranging the coating layer at a position that contacts the heat seal bar. That is, thermal shrinkage of the laminate during heat sealing can be suppressed, and heat sealing can be performed at a temperature approximately 20° C. higher than that of a laminate without a coating layer.
• the above-mentioned coat layer can be easily peeled off from the stretched polyolefin film by treating the laminate of the present invention with an alkali.
• adhesive layers, printed layers, vapor deposited layers, etc. can be peeled off or dissolved from the base material (stretched polyolefin or heat seal layer).
• the laminate of the present invention has excellent recyclability.
• the alkaline solution used for peeling off the coating layer is preferably an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, or the like.
• the sodium hydroxide aqueous solution and the potassium hydroxide aqueous solution preferably have a concentration of 0.5% by mass to 10% by mass, and more preferably a concentration of 1% by mass to 5% by mass.
• the pH is preferably 10 or more.
• the alkaline solution may contain a water-soluble organic solvent.
• water-soluble organic solvents include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), and ethylene glycol dibutyl ether.
• diethylene glycol monomethyl ether (methyl carbitol), diethylene glycol dimethyl ether, diethylene glycol monoethyl ether (carbitol), diethylene glycol diethyl ether (diethyl carbitol), diethylene glycol monobutyl ether (butyl carbitol), diethylene glycol dibutyl ether, triethylene glycol monomethyl ether, Triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, methylene dimethyl ether (methylal), propylene glycol monobutyl ether, tetrahydrofuran, acetone, diacetone alcohol, acetonylacetone, acetylacetone, ethylene glycol monomethyl ether acetate (methyl cellosolve acetate), diethylene glycol monomethyl ether acetate (methyl carbitol acetate), diethylene glycol monoethyl ether acetate (carbitol acetate), ethyl hydroxyisobutyl
• the content of the water-soluble organic solvent in the alkaline solution is preferably 0.1% by mass to 20% by mass, more preferably 1% by mass to 10% by mass.
• the alkaline solution may also contain a water-insoluble organic solvent.
• water-insoluble organic solvents include alcohol solvents such as n-butanol, 2-butanol, isobutanol, and octanol, aliphatic hydrocarbon solvents such as hexane, heptane, and normal paraffin, benzene, toluene, xylene, Aromatic hydrocarbon solvents such as alkylbenzene, halogenated hydrocarbon solvents such as methylene chloride, 1-chlorobutane, 2-chlorobutane, 3-chlorobutane, carbon tetrachloride, and ester solvents such as methyl acetate, ethyl acetate, and butyl acetate.
• Examples include ketone solvents such as , methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone, and ether solvents such as ethyl ether and butyl ether, and these may be used alone or in combination of two or more.
• ketone solvents such as , methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone
• ether solvents such as ethyl ether and butyl ether
• the alkaline solution may contain a surfactant.
• Surfactants include various anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, etc. Among these, anionic surfactants, nonionic surfactants is preferred.
• anionic surfactants include alkylbenzene sulfonates, alkylphenyl sulfonates, alkylnaphthalene sulfonates, higher fatty acid salts, sulfate ester salts of higher fatty acid esters, sulfonate salts of higher fatty acid esters, and higher alcohol ethers. Sulfuric acid ester salts and sulfonic acid salts, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, etc.
• nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and glycerin fatty acid ester.
• polyoxyethylene glycerin fatty acid ester polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkyl alkanolamide, acetylene glycol, oxyethylene adduct of acetylene glycol,
• examples include polyethylene glycol polypropylene glycol block copolymers.
• surfactants include silicone surfactants such as polysiloxane oxyethylene adducts; fluorine surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers. ; Biosurfactants such as spicrisporic acid, rhamnolipid, lysolecithin, etc. can also be used.
• surfactants can be used alone or in combination of two or more.
• the amount added is preferably in the range of 0.001 to 2% by mass, more preferably 0.001 to 1.5% by mass, and 0.01 to 1.5% by mass, based on the total amount of the alkaline solution. More preferably, the content is in the range of 1% by mass.
• Examples of methods for peeling the coating layer from the laminate of the present invention include heating the above-mentioned alkaline solution to 20 to 90 ° C., or immersing the laminate of the present invention in a state of ultrasonic vibration.
• the heating method is not particularly limited, and known heating methods using heat rays, infrared rays, microwaves, etc. can be employed.
• the ultrasonic vibration for example, a method of attaching an ultrasonic vibrator to the processing tank and imparting ultrasonic vibration to the alkaline solution can be adopted.
• the alkaline solution is stirred during immersion.
• stirring methods include a method of mechanically stirring the dispersion of the laminated film stored in the processing tank using a stirring blade, a method of water jet stirring using a water jet pump, and a method of bubbling with an inert gas such as nitrogen gas. The above-mentioned methods may be used in combination to effectively peel off the multilayer film.
• the time for immersing the laminate in the alkaline solution is, for example, in the range of 2 minutes to 48 hours, depending on the configuration of the laminate.
• the laminate of the present invention can be used as a multilayer packaging material for the purpose of protecting foods, medicines, and the like.
• the layer structure may change depending on the contents, usage environment, and usage form.
• the packaging material of the present invention is obtained, for example, by stacking the heat-sealing layers of the laminate of the present invention facing each other and then heat-sealing the peripheral edges thereof.
• the laminate of the present invention is folded or stacked so that the surfaces of the inner layers (the surfaces of the sealant film) are facing each other, and the peripheral edges are sealed, for example, by a side seal type, two-way seal type,
• Heat-sealing methods include three-sided sealing type, four-sided sealing type, envelope-sticking sealing type, gassho-sticking sealing type, pleated sealing type, flat-bottom sealing type, square-bottom sealing type, gusset type, and other heat-sealing types. It will be done.
• the packaging material of the present invention can take various forms depending on the contents, usage environment, and usage form. Freestanding packaging materials (standing pouches), etc. are also possible. Heat sealing can be performed by any known method such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing, ultrasonic sealing, or the like.
• the opening is heat-sealed to produce a product using the packaging material of the present invention.
• the contents to be filled include rice crackers, bean sweets, nuts, biscuits/cookies, wafer sweets, marshmallows, pies, half-baked cakes, candy, snack foods such as bread, snack noodles, instant noodles, dry noodles, and pasta.
• aseptically packaged cooked rice, porridge, rice porridge, wrapped mochi, staples such as cereal foods, pickles, boiled beans, natto, miso, frozen tofu, tofu, name mushrooms, konjac, processed wild vegetables, jams, peanut cream, salads, frozen
• Processed agricultural products such as vegetables and potato products, processed meat products such as hams, bacon, sausages, processed chicken products, corned beef products, fish meat hams and sausages, fish paste products, kamaboko, seaweed, tsukudani, bonito flakes, salted fish, Processed seafood products such as smoked salmon and mustard cod roe; pulp such as peaches, mandarin oranges, pineapples, apples, pears, and cherries; vegetables such as corn, asparagus, mushrooms, onions, carrots, daikon radish, and potatoes; hamburgers and meat.
• the packaging material of the present invention can also be used as a packaging material for cigarettes, disposable body warmers, pharmaceuticals such as infusion packs, cosmetics, vacuum insulation materials, and the like.
• Blend compositions and other numerical values are based on mass unless otherwise specified.
• active ingredient is the value obtained by dividing the theoretical yield (parts by weight) when all the methoxy groups of the silane monomer used undergo a hydrolysis condensation reaction by the actual yield (parts by weight) after the hydrolysis condensation reaction, That is, it is calculated using the formula: [Theoretical yield (parts by weight) when all methoxy groups of the silane monomer undergo a hydrolysis condensation reaction/Actual yield after hydrolysis condensation reaction (parts by weight)].
• the resulting reaction product was distilled under reduced pressure of 10 to 300 kPa at 40 to 60°C for 2 hours to remove generated methanol and water, and then 128.6 parts of MEK and acetic acid n- 5.8 parts of butyl was added to obtain 600 parts of a composite resin (A-2) consisting of a polysiloxane segment (a1-1) and a vinyl polymer segment (a2-1) with a nonvolatile content of 70.0%. .
• AA 1.5 parts, BA 1.5 parts, MMA 30.6 parts, BMA 29.4 parts, CHMA 75 parts, HEMA 7.5 parts, MPTS 4.5 parts, TBPEH 6.8 parts, MIBK 15 parts. was added dropwise into the reaction vessel at the same temperature with stirring under nitrogen gas flow over 4 hours, and then further stirred at the same temperature for 2 hours to obtain a number average molecular weight of 5800 and a hydroxyl value.
• a reaction solution containing a vinyl polymer having (OHv) of 64.7 mgKOH/g was obtained.
• a mixture of 0.06 parts of "A-4" and 12.8 parts of deionized water was added dropwise into the reaction vessel over 5 minutes, and the mixture was stirred at the same temperature for 5 hours to hydrolyze the silane compound.
• Preparation Example 2 Preparation of dispersion of inorganic particles (m-2) MTMS 276.8 parts, MPTS 504.8 parts, IPA-ST 4107.9 parts, "A-4" 0.7 parts, deionized water A dispersion of inorganic particles (m-2) was obtained in the same manner as in Preparation Example 1 except that 109.9 parts were used and MIBK was not used.
• Example 1 A coating agent of Example 1 was prepared by adding 50 parts of TMP3EOTA to 100 parts of composite resin (A-1) (50 parts in terms of solid content).
• Example 2 (Example 2) - (Example 4) Coating agents of Examples 2 to 4 were prepared in the same manner as in Example 1, except that the composite resin (A) used, the reactive compound, and its blending amount were changed to those shown in Table 5.
• Example 5 A mixture of 50 parts of composite resin (A-1) (25 parts in terms of solid content), 25 parts of silica particles (Aerosil 50 manufactured by Nippon Aerosil Co., Ltd., average primary particle diameter of about 30 nm), and 175 parts of MIBK was Using Ultra Apex Mill UAM015 manufactured by Kogyo Co., Ltd., zirconia beads with a diameter of 30 ⁇ m were filled in the mill as media at 50% of the mill volume, and circulatory milling was carried out for 30 minutes at a flow rate of 1.5 liters per minute. went.
• MIBK was removed using an evaporator to obtain 100 parts of a dispersion liquid of composite resin (A-1) and silica with a nonvolatile content concentration of 50%.
• a coating agent of Example 5 was prepared by adding 100 parts of TMP3EOTA thereto.
• Example 6 (Example 6) to (Example 11) Coating agents of Examples 6 to 11 were prepared in the same manner as in Example 5, except that the composite resin (A), silica particles, reactive compounds and their blending amounts were changed to those shown in Tables 5 and 6.
• Example 12 A coating agent of Example 12 was prepared by adding 35 parts of TMP3EOTA to 100 parts of composite resin (A-5) (35 parts in terms of solid content).
• Example 13 to (Example 17) Coating agents of Examples 13 to 17 were obtained in the same manner as in Example 12, except that the composite resin (A) used, the reactive compound and its blending amount were changed to those shown in Tables 6 and 7.
• TMP3EOTA was used as a coating agent in Comparative Example 2.
• Comparative example 3 A mixture of 50 parts of TMP3EOTA and 50 parts of TCDDA was used as a coating agent in Comparative Example 3.
• Comparative example 4 A mixture of 50 parts of TMP3EOTA and 125 parts of MEK-ST-40 was used as a coating agent in Comparative Example 4.
• the prepared coating agent was applied to a stretched polyethylene film (Hybron P manufactured by Tokyo Ink Co., Ltd.) with a film thickness of 25 ⁇ m at a concentration of 2 g/m 2 , and after the solvent was evaporated, energy intensity was is 125,000 eV, and the irradiation dose is 50 kGy ⁇ m/min.
• a coating layer was formed by irradiating an electron beam with (kilogray).
• the laminate of the present invention exhibited excellent adhesion, heat resistance, and recyclability.

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