Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
  • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
  • C09J123/04—Homopolymers or copolymers of ethene
  • C09J123/08—Copolymers of ethene
  • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
  • C09J123/0869—Acids or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
  • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/21—Paper; Textile fabrics
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/28—Metal sheet
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/35—Heat-activated
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
  • C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2400/00—Presence of inorganic and organic materials
  • C09J2400/10—Presence of inorganic materials
  • C09J2400/16—Metal
  • C09J2400/163—Metal in the substrate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2400/00—Presence of inorganic and organic materials
  • C09J2400/20—Presence of organic materials
  • C09J2400/28—Presence of paper
  • C09J2400/283—Presence of paper in the substrate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2423/00—Presence of polyolefin
  • C09J2423/04—Presence of homo or copolymers of ethene

Definitions

• the present invention relates to a laminated body.
• the method of bonding (that is, heat-sealing) a base material such as a plastic film, a vapor-deposited film, a metal foil, a paper, or a non-woven fabric with another adherend or a base material by heat and pressure is widely used in various industrial fields.
• a base material such as a plastic film, a vapor-deposited film, a metal foil, a paper, or a non-woven fabric with another adherend or a base material by heat and pressure
• an adhesive layer that can be bonded by heat and pressure is usually provided in advance on the base material, and the base material and another adherend, or the base materials are connected to each other via the adhesive layer. Are pasted together.
• an aqueous dispersion composition of a modified product of ethylene, ⁇ , ⁇ -unsaturated carboxylic acid and ⁇ , ⁇ -unsaturated carboxylic acid metal salt copolymer is applied. Heat sealing is performed via the formed adhesive layer.
• An object of the present invention is to provide a laminate having an adhesive layer having excellent low temperature adhesiveness, water resistance and heat resistance.
• the present invention includes the following inventions [1] to [6].
• a base material and an adhesive layer laminated on at least one surface of the base material are provided.
• the adhesive layer is obtained by drying a coating of an aqueous dispersion containing water and a resin (X).
• the total content of structural units derived from the unsaturated carboxylic acid contained in the two or more kinds of ethylene-unsaturated carboxylic acid copolymers (a) is the total content of the polymer contained in the resin (X).
• the two or more kinds of ethylene-unsaturated carboxylic acid copolymers (a) are An ethylene-unsaturated carboxylic acid copolymer (a1) having a structural unit derived from an unsaturated carboxylic acid having a content of 12% by mass or more and 30% by mass or less. [1] or containing one or more kinds of ethylene-unsaturated carboxylic acid copolymer (a2) having a content of structural units derived from unsaturated carboxylic acid of more than 0% by mass and less than 12% by mass, respectively.
• the ethylene-unsaturated carboxylic acid copolymer (a1) contains two or more kinds of ethylene-unsaturated carboxylic acid copolymers having different contents of structural units derived from the unsaturated carboxylic acid.
• the ethylene-unsaturated carboxylic acid copolymer (a2) contains two or more kinds of ethylene-unsaturated carboxylic acid copolymers having different contents of structural units derived from the unsaturated carboxylic acid.
• ethylene-unsaturated carboxylic acid copolymer (a1) Ethylene-unsaturated carboxylic acid copolymer (a1-1) having an unsaturated carboxylic acid-derived structural unit content of 17% by mass or more and 30% by mass or less
• the laminate according to [4] which comprises an ethylene-unsaturated carboxylic acid copolymer (a1-2) having a content of structural units derived from unsaturated carboxylic acid of 12% by mass or more and less than 17% by mass.
• a base material and an adhesive layer laminated on at least one surface of the base material are provided.
• the numerical range represented by using “-” means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
• the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. good.
• the laminate of the present invention comprises a base material and an adhesive layer laminated on at least one surface of the base material.
• the adhesive layer is characterized by containing two or more kinds of ethylene-unsaturated carboxylic acid copolymers (a) having different contents of structural units derived from unsaturated carboxylic acid.
• One form of the laminate of the present invention comprises a substrate and an adhesive layer laminated on at least one surface of the substrate, wherein the adhesive layer is water-dispersed containing water and a resin (X).
• the adhesive layer is water-dispersed containing water and a resin (X).
• the aqueous dispersion used for producing the laminate of the present invention contains a resin (X) and water for dispersing the resin (X).
• the resin (X) contains two or more kinds of ethylene-unsaturated carboxylic acid copolymers (a) having different contents of structural units derived from unsaturated carboxylic acid.
• the total content (acid content) of the structural unit derived from the unsaturated carboxylic acid contained in the ethylene-unsaturated carboxylic acid copolymer (a) is the monomer of the polymer contained in the resin (X). It is preferably 5% by mass or more, more preferably 8% by mass or more, preferably less than 18% by mass, and more preferably less than 16% by mass, based on the total amount of the derived structural units.
• the total content (acid content) of the structural unit derived from the unsaturated carboxylic acid is within the above range, the obtained laminate may have excellent low-temperature adhesiveness, water resistance and heat resistance.
• the total content of the structural units derived from ethylene contained in the ethylene-unsaturated carboxylic acid copolymer (a) is the total mass of the structural units derived from the monomer of the polymer contained in the resin (X). It is preferably 82% by mass or more, more preferably 84% by mass or more, preferably less than 95% by mass, and more preferably 92% by mass or less.
• the obtained laminate may have excellent low temperature adhesiveness, water resistance and heat resistance.
• the weight average molecular weight of the resin (X) is, for example, 8,000 or more, preferably 10,000 or more, for example, 150,000 or less, preferably 100,000 or less.
• the weight average molecular weight is a value obtained in terms of standard polystyrene by gel permeation chromatography (GPC) measurement.
• the melting point of the resin (X) is, for example, 80 ° C. or higher, preferably 85 ° C. or higher, and for example, 97 ° C. or lower, preferably 92 ° C. or lower.
• the melt flow rate of the resin (X) (MFR ASTM D1238, 190 ° C., 2.16 kg load) is preferably 0.1 g / 10 min or more, more preferably 0.5 g / 10 min or more, and preferably 150 g / min. It is 10 minutes or less, more preferably 100 g / 10 minutes or less.
• the method for producing the resin (X) containing two or more kinds of ethylene-unsaturated carboxylic acid copolymers (a) having different contents of structural units derived from unsaturated carboxylic acid is not particularly limited.
• the ethylene-unsaturated carboxylic acid copolymer (a) having the highest melting point has a melting point or higher, preferably 100 ° C. or higher, more preferably 100 ° C. or higher.
• the resin (X) can be produced by melt-kneading two or more kinds of ethylene-unsaturated carboxylic acid copolymers at 110 ° C. or higher.
• two or more kinds of ethylene-unsaturated carboxylic acid copolymers (a) two or more kinds of ethylene-unsaturated carboxylic acid copolymers in which some or all of the carboxy groups contained in the copolymers are neutralized.
• it can be produced by melt-kneading an inorganic base neutralized product of two or more kinds of ethylene-unsaturated carboxylic acid copolymers.
• two or more kinds of ethylene-unsaturated carboxylic acid copolymers are melt-kneaded to prepare a melt-kneaded product, and the obtained melt-kneaded product is combined with two or more kinds of ethylene-unsaturated carboxylic acids.
• polymers in an aqueous solution containing a neutralizing agent and water, preferably kept at the melting point of the ethylene-unsaturated carboxylic acid copolymer having the highest melting point or higher, more preferably 100 ° C. or higher, still more preferably 110 ° C. or higher.
• a neutralizing agent and water preferably kept at the melting point of the ethylene-unsaturated carboxylic acid copolymer having the highest melting point or higher, more preferably 100 ° C. or higher, still more preferably 110 ° C. or higher.
• Two or more kinds of ethylene-unsaturated carboxylic acid copolymers can be prepared by neutralizing a part or all of the carboxy groups.
• a basic compound can be used as the neutralizing agent.
• a basic compound includes inorganic basic compounds such as sodium hydroxide and potassium hydroxide; organic basic compounds typified by amines such as ammonia, triethylamine, triethanolamine and dimethylethanolamine; and the like.
• inorganic basic compounds are preferable, and sodium hydroxide and potassium hydroxide are more preferable.
• These basic compounds may be used alone or in combination of two or more.
• the amount of the basic compound added is, for example, 5 mol or more, preferably 20 mol or more, more preferably 25 mol, with respect to 100 mol of all the carboxy groups contained in the two or more kinds of ethylene-unsaturated carboxylic acid (a).
• the above is, for example, 70 mol or less, preferably 60 mol or less.
• the holding temperature is, for example, 40 ° C. or higher, preferably 50 ° C. or higher, and for example, 190 ° C. or lower, preferably 180 ° C. or lower.
• the holding time is, for example, 30 minutes or more, preferably 1 hour or more, for example, 12 hours or less, preferably 10 hours or less.
• the degree of neutralization of the two or more kinds of ethylene-unsaturated carboxylic acid copolymers (a) as a whole is preferably, for example, 20% or more. Is 25% or more, for example, 70% or less, preferably 60% or less.
• the degree of neutralization means the mol% in which the carboxy group in the ethylene-unsaturated carboxylic acid copolymer (a) in the resin (X) is neutralized by the basic compound which is a neutralizing agent. ..
• the degree of neutralization is within the above range, an adhesive layer having excellent heat seal strength can be obtained from the aqueous dispersion.
• the degree of neutralization is calculated according to the examples described later.
• the resin (X) may be water and two or more kinds of ethylene-unsaturated carboxylic acid copolymers (a), as well as optionally low-density polyethylene, ethylene-butene copolymer, ethylene-propylene copolymer, ethylene-.
• Each of the ethylene-unsaturated carboxylic acid copolymers contained as two or more kinds of ethylene-unsaturated carboxylic acid copolymers (a) has a structural unit derived from ethylene and a structural unit derived from unsaturated carboxylic acid. It is a copolymer containing.
• the content of the structural unit derived from the unsaturated carboxylic acid, which is a copolymer having a large carboxy group content, is 12% by mass or more and 30% by mass in the two or more kinds of ethylene-unsaturated carboxylic acid copolymer (a).
• the content of the structural unit derived from the unsaturated carboxylic acid in the ethylene-unsaturated carboxylic acid copolymer (a1) is preferably 15% by mass or more, preferably 25% by mass or less from the viewpoint of emulsion stability. Is.
• the weight average molecular weight of the ethylene-unsaturated carboxylic acid copolymer (a1) is, for example, 8,000 or more, preferably 10,000 or more, preferably 150,000 or less, preferably 150,000 or less, in terms of adhesive strength and emulsion stability. It is less than 10,000.
• the melting point of the ethylene-unsaturated carboxylic acid copolymer (a1) is, for example, 70 ° C. or higher, preferably 80 ° C. or higher, and for example, 100 ° C. or lower, preferably 95 ° C. or lower in terms of heat sealability.
• the melt flow rate (MFR ASTM D1238, 190 ° C., 2.16 kg load) of the ethylene-unsaturated carboxylic acid copolymer (a1) is, for example, 0.1 g / 10 minutes or more from the viewpoint of adhesive strength and emulsion stability. It is preferably 0.5 g / 10 minutes or more, for example, 150 g / 10 minutes or less, preferably 100 g / 10 minutes or less.
• the content of the structural unit derived from the unsaturated carboxylic acid in the ethylene-unsaturated carboxylic acid copolymer (a2) is preferably 2% by mass or more, preferably 10% by mass or less from the viewpoint of emulsion stability. Is.
• the weight average molecular weight of the ethylene-unsaturated carboxylic acid copolymer (a2) is, for example, 8,000 or more, preferably 10,000 or more, preferably 150,000 or less, preferably 150,000 or less, in terms of adhesive strength and emulsion stability. It is 100,000 or less.
• the melting point of the ethylene-unsaturated carboxylic acid copolymer (a2) is, for example, 70 ° C. or higher, preferably 80 ° C. or higher, and for example 100 ° C. or lower, preferably 95 ° C. or lower, from the viewpoint of heat sealability.
• the melt flow rate (MFR ASTM D1238, 190 ° C., 2.16 kg load) of the ethylene-unsaturated carboxylic acid copolymer (a2) is, for example, 0.1 g / 10 minutes or more from the viewpoint of adhesive strength and emulsion stability. It is preferably 0.5 g / 10 minutes or more, for example, 150 g / 10 minutes or less, preferably 100 g / 10 minutes or less.
• two or more kinds of ethylene-unsaturated carboxylic acid copolymers (a) satisfy at least one of the following conditions (i) and (ii) from the viewpoint of low temperature adhesiveness, water resistance and heat resistance.
• the ethylene-unsaturated carboxylic acid copolymer (a1) contains two or more kinds of ethylene-unsaturated carboxylic acid copolymers having different contents of structural units derived from the unsaturated carboxylic acid.
• the ethylene-unsaturated carboxylic acid copolymer (a2) contains two or more kinds of ethylene-unsaturated carboxylic acid copolymers having different contents of structural units derived from the unsaturated carboxylic acid.
• the content of the structural unit derived from the unsaturated carboxylic acid is 17% by mass or more and 30% by mass or less of the ethylene-unsaturated carboxylic acid. It is preferable to contain an acid copolymer (a1-1) and an ethylene-unsaturated carboxylic acid copolymer (a1-2) having an amount of 12% by mass or more and less than 17% by mass.
• the content of the structural unit derived from the unsaturated carboxylic acid in the ethylene-unsaturated carboxylic acid copolymer (a1-1) is preferably 18% by mass or more, preferably 25% by mass, from the viewpoint of emulsion stability. % Or less.
• the weight average molecular weight of the ethylene-unsaturated carboxylic acid copolymer (a1-1) is, for example, 8,000 or more, preferably 10,000, for example, 150,000 or less, preferably 150,000 or less, in terms of adhesive strength and emulsion stability. Is 100,000 or less.
• the melting point of the ethylene-unsaturated carboxylic acid copolymer (a1-1) is, for example, 70 ° C. or higher, preferably 80 ° C. or higher, and for example, 100 ° C. or lower, preferably 95 ° C. or lower in terms of heat sealability. be.
• the melt flow rate (MFR ASTM D1238, 190 ° C., 2.16 kg load) of the ethylene-unsaturated carboxylic acid copolymer (a1-1) is, for example, 0.1 g / 10 from the viewpoint of adhesive strength and emulsion stability. Minutes or more, preferably 0.5 g / 10 minutes or more, for example 150 g / 10 minutes or less, preferably 100 g / 10 minutes or less.
• the content of the structural unit derived from the unsaturated carboxylic acid in the ethylene-unsaturated carboxylic acid copolymer (a1-2) is preferably 12% by mass or more, preferably 15% by mass, from the viewpoint of emulsion stability. % Or less.
• the weight average molecular weight of the ethylene-unsaturated carboxylic acid copolymer (a1-2) is, for example, 8,000 or more, preferably 10,000, for example, 150,000 or less, preferably 150,000 or less, in terms of adhesive strength and emulsion stability. Is 100,000 or less.
• the melting point of the ethylene-unsaturated carboxylic acid copolymer (a1-2) is, for example, 70 ° C. or higher, preferably 80 ° C. or higher, and for example, 100 ° C. or lower, preferably 95 ° C. or lower in terms of heat sealability. be.
• the melt flow rate (MFR ASTM D1238, 190 ° C., 2.16 kg load) of the ethylene-unsaturated carboxylic acid copolymer (a1-2) is, for example, 0.1 g / 10 from the viewpoint of adhesive strength and emulsion stability. Minutes or more, preferably 0.5 g / 10 minutes or more, for example 150 g / 10 minutes or less, preferably 100 g / 10 minutes or less.
• the ethylene-unsaturated carboxylic acid copolymer (a) the above-mentioned ethylene-unsaturated carboxylic acid copolymer (a1-1), ethylene-unsaturated carboxylic acid copolymer (a1-2) and ethylene-.
• the unsaturated carboxylic acid copolymer (a2) the ethylene-unsaturated carboxylic acid copolymer weight is relative to the total amount of the ethylene-unsaturated carboxylic acid copolymer (a) contained in the resin (X).
• the content of the coalescence (a2) is preferably 20% by mass or more, more preferably 25% by mass or more, preferably 85% by mass or less, and more preferably 80% by mass or less.
• the content of the ethylene-unsaturated carboxylic acid copolymer (a1-1) is preferably 20% by mass with respect to the total amount of the ethylene-unsaturated carboxylic acid copolymer (a) contained in the resin (X). As described above, it is more preferably 25% by mass or more, preferably 80% by mass or less, and more preferably 75% by mass or less.
• the content of the ethylene-unsaturated carboxylic acid copolymer (a1-2) is preferably 10% by mass with respect to the total amount of the ethylene-unsaturated carboxylic acid copolymer (a) contained in the resin (X).
• the total content of the ethylene-unsaturated carboxylic acid copolymer (a1-1), the ethylene-unsaturated carboxylic acid copolymer (a1-2) and the ethylene-unsaturated carboxylic acid copolymer (a2) is It is 100% by mass.
• Each ethylene-unsaturated carboxylic acid copolymer contained in two or more kinds of ethylene-unsaturated carboxylic acid copolymers (a) depends on the content of the structural unit derived from the desired unsaturated carboxylic acid. It is obtained by polymerizing a monomer component containing ethylene and an unsaturated carboxylic acid.
• the unsaturated carboxylic acid is a monomer having at least one ethylenically unsaturated bond and a carboxy group.
• the unsaturated carboxylic acid include monobasic acids having ethylenically unsaturated bonds such as acrylic acid, methacrylic acid and crotonic acid; and dibasic acids having ethylenically unsaturated bonds such as maleic acid, fumaric acid and itaconic acid. ; And so on.
• monobasic acid having an ethylenically unsaturated bond is preferable, and acrylic acid and methacrylic acid are more preferable, from the viewpoint of water resistance.
• These unsaturated carboxylic acids may be used alone or in combination of two or more.
• the content ratio of ethylene in the monomer component may be appropriately set according to the content of the constituent unit derived from ethylene of the obtained ethylene-unsaturated carboxylic acid copolymer.
• the content ratio of the unsaturated carboxylic acid in the monomer component may be appropriately set according to the content of the structural unit derived from the unsaturated carboxylic acid of the ethylene-unsaturated carboxylic acid copolymer.
• the polymerization method of the monomer component is not particularly limited as long as a desired ethylene-unsaturated carboxylic acid copolymer can be obtained, and examples of the polymerization method include known polymerization methods.
• the ethylene-unsaturated carboxylic acid copolymer can be obtained, for example, by contacting and polymerizing a monomer component with a polymerization initiator such as a peroxide under high temperature and high pressure conditions.
• the ethylene-unsaturated carboxylic acid copolymer can be obtained as a dispersion (aqueous dispersion) in which the particles are dispersed in water.
• a dispersion aqueous dispersion
• the ethylene-unsaturated carboxylic acid copolymer has a self-emulsifying property.
• the aqueous dispersion is, for example, a dispersion (aqueous dispersion) in which resin particles of a resin (X) containing two or more kinds of ethylene-unsaturated carboxylic acid copolymers (a) are dispersed in water as described above. Can be obtained as. Specifically, the resin component containing two or more kinds of ethylene-unsaturated carboxylic acid copolymers is dispersed in water kept at preferably 100 ° C. or higher, more preferably 110 ° C. or higher, or in an alkaline aqueous solution and stirred. It can be manufactured by doing so.
• the aqueous dispersion obtained as described above may contain an additive in addition to the resin (X).
• the additive include the above-mentioned emulsifier, curing agent, cross-linking agent, film-forming auxiliary, defoaming agent, repellent inhibitor, leveling agent, tackifier, hardness-imparting agent, preservative, thickener, antifreeze.
• Agents, dispersants, inorganic pigments, organic pigments and the like can be mentioned.
• These additives may be used alone or in combination of two or more. The amount of these additives added and the timing of the addition thereof are appropriately set according to the purpose and use.
• the melt flow rate of the resin (X) (MFR ASTM D1238, 190 ° C., 2.16 kg load) is preferably 0.1 g / 10 min or more, more preferably 0.5 g / 10 min or more, and preferably 150 g / min. It is 10 minutes or less, more preferably 100 g / 10 minutes or less.
• the weight average particle size (measurement method: light scattering measurement) of the resin particles of the resin (X) dispersed in the aqueous dispersion is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, and preferably 4. It is preferably 0 ⁇ m or less, more preferably 1.0 ⁇ m or less.
• the viscosity of the aqueous dispersion is preferably 10 mPa ⁇ s or more, more preferably 50 mPa ⁇ s or more, preferably 900 mPa ⁇ s or less at 25 ° C. from the viewpoint of coating suitability. More preferably, it is 500 mPa ⁇ s or less.
• the non-volatile content (solid content concentration) of the aqueous dispersion is preferably 20% by mass or more, more preferably 25% by mass or more, preferably 60% by mass or less, and more preferably 55% by mass or less.
• the non-volatile content of the aqueous dispersion is a ratio of the component containing the resin component remaining when the water of the aqueous dispersion is removed by heating or the like to the aqueous dispersion.
• the aqueous dispersion can be suitably used for forming an adhesive layer (heat seal layer) of the laminated body.
• the laminate having such an adhesive layer is excellent in low temperature adhesiveness, water resistance and heat resistance.
• the laminate of the present invention has a base material and an adhesive layer that can be produced from the above-mentioned aqueous dispersion on at least one surface of the base material.
• this adhesive layer contains two or more kinds of ethylene-unsaturated carboxylic acid copolymers (a) having different contents of structural units derived from unsaturated carboxylic acid.
• the adhesive layer may be present on one side of the base material or may be present on both sides. Further, the adhesive layer may be present on the entire surface of the base material or may be present on a part of the base material.
• base material examples include cellophane, polyethylene, ethylene-vinyl acetate copolymer, ionomer, polypropylene, polyamide (nylon), polyester, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and polycarbonate.
• Plastic films made of plastic materials such as, polystyrene, polyacrylonitrile copolymers, and mixtures thereof; on these plastic films, metals such as aluminum, gold, silver, copper, nickel, zinc, titanium, cobalt, indium, chromium, etc. , Or a vapor-deposited film obtained by depositing a vapor-deposited material such as aluminum oxide or an inorganic oxide of silicon oxide on a plastic film; metal foil such as aluminum foil, paper, non-woven fabric, and the like.
• the paper that can be the base material of the laminate is not particularly limited, and known paper containing pulp as a main component can be used.
• the pulp that is the main component of paper include chemical pulps such as LBKP (broadwood bleached kraft pulp) and NBKP (coniferous bleached kraft pulp); GP (crushed wood pulp), PGW (pressurized crushed wood pulp), and RMP (refiner mechanical).
• Mechanical pulp such as pulp), TMP (thermomechanical pulp), CTMP (chemithermomechanical pulp), CMP (chemimechanical pulp), CGP (chemigrand pulp); wood pulp such as DIP (deinking pulp); Kenaf, Bagus , bamboo, non-wood pulp such as cotton; etc.
• the density of these paper substrates is preferably 0.5 g / m 3 or more, and more preferably 0.7 g / m 3 or more.
• a pulp containing 90 to 100% by mass of LBKP hardwood bleached kraft pulp
• LBKP hardwood bleached kraft pulp
• the pulp may contain synthetic fibers as long as the effects of the present invention are not impaired. From the viewpoint of environmental conservation, among the pulps, ECF (Elemental Chlorine Free) pulp, TCF (Total Chlorine Free) pulp, recycled paper pulp, and pulp obtained from planted trees are preferable.
• ECF Exponal Chlorine Free
• TCF Total Chlorine Free
• the beating degree of the pulp is Canadian standard freeness (JIS P 8121: 1995 "Pulp freshness test method"), for example, 200 to 700 ml CSF, preferably 450 to 620 ml CSF.
• Paper containing a filler can also be used as the base paper.
• the filler include light calcium carbonate, heavy calcium carbonate, talc, clay, kaolin, calcined clay, titanium dioxide, and aluminum hydroxide.
• the filler content in the paper is, for example, 1 to 30 parts by mass with respect to 100 parts by mass of the dry mass of the pulp.
• light calcium carbonate is contained as a filler, it is preferable to contain 1 to 10 parts by mass of light calcium carbonate with respect to 100 parts by mass of dry mass of pulp.
• the paper may contain various known additives for papermaking in addition to pulp.
• the papermaking additive include an internal paper strength enhancer such as a sizing agent and a wet paper strength enhancer; a bulking agent, a yield improver, a drainage improver, a coloring dye, a coloring pigment, a fluorescent whitening agent, and fluorescence. Examples include a decoloring agent and a pitch control agent.
• the paper as the base material may be paper coated with a water-soluble polymer such as starch, polyvinyl alcohol, or polyacrylamide.
• the method of making the base paper is not particularly limited, and for example, a long net paper machine, a long net multi-layer paper machine, a circular net paper machine, a circular net multi-layer paper machine, a long net circular net combination multi-layer paper machine, and a twin wire paper machine.
• Paper can be manufactured by various paper machines such as machines.
• the paper used in the laminated body of the present invention may be a single-layer paper, a multi-layer paper, or a laminated product having a plurality of layers.
• metal foil such as aluminum foil, paper, non-woven fabric, plastic film and vapor-deposited film are preferable, and metal foil such as aluminum foil is preferable from the viewpoint of being superior in heat-sealing property of the adhesive layer contained in the laminate. And paper are more preferred.
• the base material may be used alone or in combination of two or more.
• the base material may be subjected to pretreatment such as primer (titanate, polyethyleneimine, etc.) treatment, corona discharge treatment, chemical conversion treatment, etc. for the purpose of improving the adhesion to the adhesive layer.
• the base material may be provided with one or more layers different from the adhesive layer.
• one or more coating layers may be provided.
• examples of such a coating layer include a pigment coating layer obtained from a coating liquid containing a pigment and an adhesive.
• a known pigment used for the coating layer of general printing coating paper can be used, and for example, calcium carbonate (heavy calcium carbonate, light calcium carbonate, etc.) can be used.
• Kaolin including clay), calcined clay, talc, magnesium carbonate, barium sulfate, calcium sulfate, titanium dioxide, zinc oxide, zinc sulfate, zinc carbonate, calcium silicate, aluminum silicate, magnesium silicate, diatomaceous soil, aluminum hydroxide, water
• Inorganic pigments such as magnesium oxide
• organic pigments such as acrylic resins, styrene resins, vinyl chloride resins, nylons, and resins obtained by copolymerizing the monomers constituting these resins (so-called plastic pigments). Be done.
• the pigment used for the pigment coating layer for example, a combination of 20 to 40 parts by mass of kaolin and 60 to 80 parts by mass of heavy calcium carbonate can be used.
• the adhesive used for the pigment coating layer a known adhesive used for the coating layer of general printing coated paper can be used, and for example, a butadiene-based copolymerized latex and a cross-linking agent-modified starch can be used.
• Oxidized starch Oxidized starch, enzyme-modified starch, esterified starch, etherified starch, cationic starch, amphoteric starch and other starches; water-soluble polymers such as gelatin, casein, soybean protein and polyvinyl alcohol; vinyl acetate, ethylene vinyl acetate, Examples thereof include synthetic resins of polyurethane-based resin, acrylic-based resin, polyester-based resin, and polyamide-based resin.
• the blending ratio of the pigment and the adhesive in the pigment coating layer is not particularly limited, but is preferably 5 to 50 parts by mass of the adhesive with respect to 100 parts by mass of the pigment.
• a combination of 1 to 5 parts by mass of phosphoric acid esterified starch and 5 to 15 parts by mass of a styrene butadiene latex adhesive can be used with respect to 100 parts by mass of the pigment.
• the pigment coating layer may contain various auxiliaries as long as the effects of the present invention are not impaired.
• a viscosity modifier for example, a softener, a gloss-imparting agent, a water resistant agent, a dispersant, and a flow modifier.
• the amount of the coating liquid for producing such a pigment coating layer is, for example, 2 to 40 g / m 2 in terms of non-volatile content (solid content conversion) per one side of the base paper.
• the adhesive layer contained in the laminate of the present invention is, for example, coated (coated) with an aqueous dispersion containing a resin (X) on at least one surface of the substrate, and the layer made of this coated material is dried. Then, it is obtained by removing volatile substances such as water contained in at least a part of the aqueous dispersion.
• the method for applying (coating) the aqueous dispersion obtained in the present invention is not particularly limited, and for example, a die coat method, a flow coat method, a spray coat method, a bar coat method, a gravure coat method, a gravure reverse coat method, and a kiss.
• Reverse coat method, micro gravure coat method, roll coat method, blade coat method, rod coat method, roll doctor coat method, air knife coat method, comma roll coat method, reverse roll coat method, transfer roll coat method, kiss roll coat method Examples include the curtain coat method and the printing method.
• the drying conditions for the layer made of the coating material of the aqueous dispersion are not particularly limited as long as the conditions are such that volatile components such as water derived from the aqueous dispersion can be removed, and the drying temperature is, for example, 100 to 200 ° C.
• the drying time is, for example, 10 seconds to 30 minutes.
• the amount of the adhesive layer applied may be appropriately set according to the desired application, but is preferably 1.5 g / m 2 or more, more preferably 2.0 g / m 2 or more, and preferably 13 g / m. 2 or less, preferably 10 g / m 2 or less.
• the ratio of the resin (X) in the adhesive layer may be appropriately set according to a desired application and the like, but is preferably 50% by mass or more, more preferably 80% by mass or more.
• Cobb 300 (Cobb method: contact time of JIS P8140 for 300 seconds) is preferably 15 g / m 2 or less, more preferably 10 g / m 2 or less.
• the adhesive layer has excellent heat-sealing properties at low temperatures. Further, it is produced from an aqueous dispersion having the above resin particles. When the adhesive layer is produced from such an aqueous dispersion, the amount of the organic solvent remaining in the adhesive layer is small, and the amount of the residual organic solvent in the adhesive layer can be preferably 100 ppm or less, more preferably 10 ppm or less.
• the laminate obtained by the present invention is suitably used as a material for heat sealing in various industrial fields.
• the base material contained in the laminate of the present invention and the adherend layer are attached via the adhesive layer.
• the adherend layer may be contained in the laminated body of the present invention, or may be a layer contained in an article different from the laminated body of the present invention.
• the adherend layer may be the same as the base material contained in the laminated body.
• a metal foil such as aluminum foil, paper, a non-woven fabric, a plastic film and a vapor-deposited film are preferable, and a metal foil such as aluminum foil and paper are more preferable.
• These adherend layers may be used alone or in combination of two or more.
• the laminate of the present invention may include the adherend layer in addition to the base material and the adhesive layer.
• the base material and the adherend layer may be attached via the adhesive layer.
• the adherend layer is laminated on the surface of the adhesive layer opposite to the surface in contact with the base material.
• the method of heat-sealing the base material and the adherend layer is not particularly limited.
• heat sealing can be performed by superimposing the base material and the adherend layer contained in the laminate via the adhesive layer, and then heating and pressurizing the layers.
• the adherend layer further has an adhesive layer
• the adhesive layer contained in the laminate of the present invention and the adhesive layer of the adherend layer are overlapped with each other, and then.
• Heat sealing may be performed by heating and pressurizing.
• the heating temperature at the time of heat sealing is, for example, 80 ° C. or higher, preferably 100 ° C. or higher, for example 250 ° C. or lower, preferably 200 ° C. or lower.
• the pressure for heat sealing is, for example, 50 kPa or more, preferably 100 kPa or more, for example, 500 kPa or less, preferably 300 kPa or less.
• the adhesive strength between the base material and the adherend layer contained in the laminate of the present invention can be evaluated by the peel strength between the base material and the adherend layer.
• the peel strength between the substrate and the adherend layer peeled at a tensile speed of 50 mm / min and 180 degrees is preferably 400 g / min. It is 15 mm or more, more preferably 500 g / 15 mm or more.
• a laminate in which the adherend layer is laminated on at least one surface of the adhesive layer contained in the laminate (in other words, an adherend on at least one surface of the adhesive layer contained in the laminate).
• the laminated body in which the layers are laminated) is included in the laminated body of the present invention regardless of the heat-sealed state (that is, before and after the heat-sealing).
• the laminate obtained by the present invention has excellent low temperature adhesiveness, water resistance and heat resistance.
• an aqueous dispersion is used to form the adhesive layer and no dispersion in which resin particles are dispersed in organic solvents such as ethyl acetate and toluene is used, the amount of residual organic solvent is extremely small. It can be suppressed. Therefore, the laminate can be suitably used as a packaging material in various industrial fields. For example, it can be suitably used as a packaging material for various industrial products such as confectionery, tea leaves, spices and other foods; tobacco, fragrances and the like; pharmaceuticals and papers.
• the average value (acid content average value) of the content of the structural unit derived from methacrylic acid in the resin 1 was 12.5% by mass, and the weight average particle size of the resin particles 1 was 0.5 ⁇ m.
• the viscosity of the aqueous dispersion 1 was 400 mPa ⁇ s, the non-volatile content (Nv) was 35%, and the melt flow rate (MFR) was 3.0 g / 10 minutes.
• a 3.5% aqueous solution of potassium hydroxide is continuously supplied at a rate of 28 g / min from the provided supply port, continuously extruded at a heating temperature of 110 ° C., and the extruded resin mixture is installed in the same extruder port.
• the water dispersion 4 was obtained by cooling the mixture to 90 ° C. with a static mixer with a jacket and further adding the mixture to warm water at 80 ° C.
• the weight average particle size of the resin particles 4 was 0.9 ⁇ m.
• the viscosity of the aqueous dispersion 4 was 300 mPa ⁇ s, the non-volatile content (Nv) was 37%, and the melt flow rate (MFR) was 1.0 g / 10 minutes.
• Example 1 Using Tami Nadu Newsprint and Papers base paper for cups (basis weight 170 g / m 2 ) as a base material, the aqueous dispersion 1 was coated twice with an air knife coater so that the resin coating amount was 6 g / m 2. It was coated and dried at 130 ° C. for 20 seconds to obtain a laminated paper-coated product 1.
• the aqueous dispersion 1 was coated once with a bar coater so that the resin coating amount was 3 g / m 2, and dried at 120 ° C. for 20 seconds.
• An aluminum foil 1 which is a laminated body was obtained.
• the aluminum foil 1 was cut into squares having a length and width of 5 cm, the coated surfaces were overlapped with each other, and the blocking resistance under the conditions of 45 ° C., 250 g / cm 2 and 24 hours was evaluated according to the criteria in Table 3. The results are shown in Table 4.
• Example 2 to 4 Paper coated products 2 to 4 and aluminum foils 2 to 4 were obtained in the same manner as in Example 1 except that the above water dispersions 2 to 4 were used instead of the water dispersion 1 in Example 1. Using the obtained paper-coated product and aluminum foil, the physical characteristics of Examples 2 to 4 were evaluated in the same manner as in Example 1 above. The results are shown in Table 4.
• Comparative Examples 1 to 3 Paper coated products 5 to 7 and aluminum foils 5 to 7 were obtained in the same manner as in Example 1 except that the above water dispersions 5 to 7 were used instead of the water dispersion 1 in Example 1. Using the obtained paper-coated product and aluminum foil, the physical characteristics of Comparative Examples 1 to 3 were evaluated in the same manner as in Example 1 above. The results are shown in Table 4.
• the acid content was measured by subjecting the resin to a debase treatment, melting it in tetrahydrofuran when heated, and titrating it with potassium hydroxide having a specified concentration in a heated state, and calculating the average acid content.
• the infrared absorption spectrum of the sample is measured, and the peak height a of absorption of 1700 cm -1 corresponding to the carboxy group is obtained.
• the peak height a corresponds to the number of unionically bonded carboxy groups in the resin.
• the sample is brought into contact with hydrochloric acid to remove metal ions in the resin (demetallation) to obtain an acid copolymer without ionic bonding (intermolecular cross-linking).
• the infrared absorption spectrum of the sample of this acid copolymer is measured, and the peak height b of absorption of 1700 cm -1 is obtained.
• the peak height b corresponds to the number of all carboxy groups in the resin.
• viscosity The viscosity was measured at 25 ° C. using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd.).
• the average particle size of the resin particles was measured by Nanotrack WaveII (Microtrac Bell).
• melt flow rate The melt flow rate (MFR) was measured according to ASTM D1238-65T under the conditions of 190 ° C. and 2.16 kg load.

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• 2021
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