Primer composition for decorative material

Abstract

To provide a primer composition for a decorative material which has good adhesion to a substrate, good adhesion to an adhesive, and good blocking resistance.SOLUTION: A primer composition for forming a primer layer of a decorative material sequentially having a substrate, the primer layer, and an adhesive layer in contact with the primer layer contains a urethane resin and a cellulose acetate-based resin. The cellulose acetate-based resin is cellulose acetate propionate and / or cellulose acetate butyrate.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a primer composition for cosmetic materials and a cosmetic material.

[0002] More specifically, the present invention relates to a cosmetic material and a primer composition for an adhesive used in the cosmetic material.

Background Art

[0003] Conventionally, in order to enhance the added value, exterior and interior decorations of means of transportation such as automobiles, buses, trains, and airplanes, exterior and interior decorations of buildings such as houses, condominiums, commercial facilities, hospitals, and community halls, and further exterior decorations of home appliances such as refrigerators and washing machines have been decorated by directly applying or spraying a so-called paint on a metal steel plate, plastic, wooden board, etc. that serves as a decorative substrate (support) through a painting or spraying process. However, the decoration by the above-described process can basically perform only a single-color decoration, and there is a problem in productivity due to the long time required for the decoration process. Furthermore, there are problems such as spraying more paint than necessary for decoration and discarding the excess, as well as the amount of energy and environmental load in the paint drying process.

[0004] In view of such problems, in recent years, there is a method of attaching a printed matter obtained by gravure printing a printing ink on a substrate to a decorative substrate. As a result, not only a single color but also a decoration with a design such as a pattern, gradation, geometric pattern, painting, or wood grain can be performed, so that an improvement in added value, productivity improvement, and reduction of environmental load can be expected. Such a cosmetic material can be obtained by attaching a printed matter having a printed pattern on a substrate to a decorative substrate via an adhesive. Here, depending on the types of the substrate and the decorative substrate, it is difficult to bond all materials with sufficient adhesive strength using an adhesive, and therefore, a primer layer for sufficiently bonding the adhesive to the substrate is required.

[0005] Patent Document 1 describes an invention related to a decorative sheet in which a primer layer for bonding to a substrate, an adhesive layer, and a support are provided on one surface of a substrate made of a polyolefin resin sheet, and a decorative layer such as a pattern printing layer is provided on the other surface of the polyolefin resin sheet. A mixture of a polyurethane resin and nitrocellulose is used as the primer for the substrate adhesive. In a printed matter having a decorative layer, a substrate, and a primer layer in this order, which is bonded to the support, when a urethane resin is used in the primer layer, there is a concern that the decorative layer and the primer layer may block. In Patent Document 1, a mixture of a polyurethane-based resin and nitrocellulose is used in the primer layer, and it is considered that blocking resistance can be ensured to a certain extent. However, it is conceivable that the primer layer may deteriorate and discolor during long-term storage of the printed matter, and the adhesion to the substrate or the adhesive may deteriorate.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] An object of the present invention is to provide a primer composition for decorative materials having good adhesion to a substrate (hereinafter also referred to as substrate adhesion) and good adhesion to an adhesive (hereinafter also referred to as adhesive adhesion), and further having good blocking resistance.

Means for Solving the Problems

[0008] As a result of intensive studies on the above problems, the present inventor has found that the above problems can be solved by using the packaging material described below, and has completed the present invention.

[0009] The present invention is a primer composition for forming the primer layer of a decorative material having a substrate, a primer layer, and an adhesive layer in contact with the primer layer in this order, Relates to a primer composition containing a urethane resin and a cellulose acetate resin.

[0010] The present invention also relates to the primer composition, wherein the base cellulose acetate resin is cellulose acetate propionate and / or cellulose acetate butyrate.

[0011] The present invention also relates to the primer composition, wherein the urethane resin contains at least one selected from the group consisting of polyester-based urethane resins, polyether-based urethane resins, acrylic-based urethane resins, and polycarbonate-based urethane resins.

[0012] The present invention also relates to the primer composition further containing a vinyl chloride copolymer resin.

[0013] The present invention also relates to the primer composition further containing fine particles.

[0014] The present invention also relates to the primer composition, wherein the fine particles are silica.

[0015] The present invention also relates to the primer composition further containing wax.

[0016] The present invention also relates to a method for manufacturing a decorative material having a base material, a primer layer, and an adhesive layer in sequence, including step (1) of applying a primer composition on the base material to form a primer layer, and step (2) of applying an adhesive on the primer layer to form the adhesive layer, relates to a method for manufacturing a decorative material, wherein the primer composition contains a urethane resin and a cellulose acetate resin.

Advantages of the Invention

[0017] According to the present invention, it has become possible to provide a primer composition for decorative materials having good adhesion to a base material and good adhesion to an adhesive, and further having good blocking resistance.

Mode for Carrying Out the Invention

[0018] Examples will be given below to explain the embodiments of the present invention in detail. However, the matters described below are examples or representative examples of the embodiments of the present invention, and the present invention is not limited to these contents unless it exceeds the gist thereof. Hereinafter, the “primer composition” may sometimes be simply expressed as “composition”, which is synonymous.

[0019] The present invention relates to a primer composition for forming the primer layer of a decorative material having a base material, a primer layer, and an adhesive layer in this order, wherein the primer layer and the adhesive layer are in contact with each other, and by using a primer composition containing a urethane resin and a cellulose acetate resin, it is possible to provide a decorative material having good adhesion to the base material and the adhesive, and further having good blocking resistance.

[0020] In the primer composition, the urethane resin and the cellulose acetate resin are uniformly dissolved by a medium such as an organic solvent. However, when the primer composition is printed on the base material and dried, the cellulose acetate resin is considered to localize on the surface of the primer layer in a form similar to layer separation with the urethane resin. In addition, in a state where a printed matter having a decorative layer, a base material, and a primer layer in this order is stacked in a continuous printed roll or sheets, the cellulose acetate resin of the primer layer and the decorative layer are in contact with each other. The cellulose acetate resin alone does not have adhesion to the base material, but has the property of being less likely to block with the decorative layer. Therefore, by using a primer composition containing a urethane resin and a cellulose acetate resin, the effect of achieving both adhesion to the base material and blocking resistance can be exhibited. In addition, it is considered that the cellulose acetate resin is less likely to deteriorate unlike nitrocellulose. However, the above functions are based on speculation and do not particularly limit the present invention.

[0021] <Primer Composition> The primer composition of the present invention forms a primer layer of a cosmetic material, contains a urethane resin, and contains a cellulose acetate resin. By using the urethane resin, the adhesion to the substrate is improved. Also, by using the cellulose acetate resin, the printability during printing (the coating film adhering to the guide roll) and the blocking resistance during storage of the printed matter are improved. The urethane resin etc. also function as a binder resin. The coating film adhering to the guide roll means that when the primer layer comes into contact with the guide roll in the printing machine during printing, part or all of the primer layer migrates to the guide roll. If the adhesion of the primer layer to the guide roll is poor, not only the guide roll will be contaminated, but also the performance of the primer layer will not be fully exhibited. From the viewpoint of adhesion to the substrate and the adhesive, it is preferable that the resin component containing the urethane resin is contained in the solid content of the composition at 20 to 95% by mass, more preferably 40 to 80% by mass, and even more preferably 50 to 70% by mass. Note that the solid content refers to the total mass of the non-volatile components of the composition.

[0022] <Resin component> The primer composition of the present invention only needs to contain a urethane resin and a cellulose acetate resin as resin components, and it is also suitable to further have a combined resin. Examples of the combined resin include polyolefin resins such as polyethylene-based resins and chlorinated polypropylene-based resins, poly(meth)acrylic-based resins, polyvinyl chloride-based resins, polyvinyl acetate-based resins, vinyl chloride-vinyl acetate copolymers, polystyrene-based resins, styrene-butadiene copolymers, styrene-maleic acid copolymers, vinylidene fluoride-based resins, polyvinyl alcohol-based resins, polyvinyl acetal-based resins, polyvinyl butyral-based resins, polybutadiene-based resins, polyester-based resins, polyamide-based resins, alkyd-based resins, epoxy-based resins, unsaturated polyester-based resins, thermosetting poly(meth)acrylic-based resins, melamine-based resins, urea-based resins, polyurethane-based resins, phenol-based resins, xylene-based resins, maleic acid resins, cellulose-based resins such as acetyl butyl cellulose and ethyl oxyethyl cellulose, rubber-based resins such as chlorinated rubber and cyclized rubber, petroleum-based resins, natural resins such as rosin and casein, etc. Among them, a vinyl chloride copolymer resin is preferably used. By using the vinyl chloride copolymer resin, the adhesion to the substrate becomes good. The vinyl chloride copolymer resin is preferably a vinyl chloride-vinyl acetate copolymer resin and a vinyl chloride-acrylic copolymer resin, and more preferably a vinyl chloride-vinyl acetate copolymer resin. Also, from the viewpoints of substrate adhesion, printability, and blocking resistance, the ratio of the urethane resin to the vinyl chloride copolymer resin is preferably 100:1 to 100:50, more preferably 100:5 to 100:30, and even more preferably 100:10 to 100:25 in terms of the weight ratio of the solid content.

[0023] <Urethane resin> In the present invention, the urethane resin preferably has polyol and isocyanate compound as constituent units, and preferably contains at least one of polyester polyol, polyether polyol, and polycarbonate polyol as the polyol. That is, as the form of the urethane resin, it preferably contains at least one selected from the group consisting of polyester-based urethane resins, polyether-based urethane resins, and polycarbonate-based urethane resins. Among them, a polyester-based urethane resin is preferably used. The structural unit derived from the polyol in the urethane resin in the present invention preferably contains at least one of a polyester polyol, a polyether polyol, and a polycarbonate polyol in an amount of 30% by mass or more, more preferably 50% by mass or more, and still more preferably 70% by mass or more in the total mass of the structural units derived from the polyol. The polyol is preferably a polyester polyol. Among the total mass of the resin components contained in the primer composition, the content of the urethane resin is preferably 50 to 95% by mass, still preferably 60 to 90% by mass, and still more preferably 65 to 85% by mass.

[0024] The number average molecular weight of the polyol is calculated from the hydroxyl value with the terminal being a hydroxyl group and is determined by (Formula 1). (Formula 1) Number average molecular weight = 56110 × number of hydroxyl groups (pieces) / hydroxyl value (mgKOH / g) In the formula, the number of hydroxyl groups refers to the number of hydroxyl groups in one molecule of the polyol, and the hydroxyl value refers to the measured value according to JIS K0070 (1992). The parentheses represent the unit.

[0025] Examples of the polyester polyol include condensates obtained by an esterification reaction of a dibasic acid and a diol, or dehydration condensates of cyclic esters such as lactones. The number average molecular weight of the polyester polyol is preferably 500 to 10000, more preferably 700 to 7000, and still more preferably 1000 to 5000. In the condensate obtained by the esterification reaction of a dibasic acid and a diol, examples of the dibasic acid include adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, pimelic acid, azelaic acid, sebacic acid, suberic acid, glutaric acid, 1,4-cyclohexyl dicarboxylic acid, dimer acid, hydrogenated dimer acid, and the like. Examples of the diol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 3,3,5-trimethylpentanediol, 2,4-diethyl-1,5-pentanediol, 1,12-octadecanediol, 1,2-alkanediol, 1,3-alkanediol, 1-monoglyceride, 2-monoglyceride, 1-monoglycerin ether, 2-monoglycerin ether, dimer diol, hydrogenated dimer diol, and the like.

[0026] Among them, diols having a branched structure are preferred. The branched structure means a diol having an alkyl side chain in which at least one hydrogen atom of the alkylene group contained in the diol is substituted by an alkyl group, and examples include propylene glycol, 1,3-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,4-pentanediol, 3-methyl-1,5-pentanediol, 2,5-hexanediol, 2-methyl-1,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, and 2,2,4-trimethyl-1,6-hexanediol. These are particularly preferred for improving printability and blocking resistance. These polyester polyols can be used alone or in combination of two or more. As the dibasic acid, sebacic acid and adipic acid are particularly preferred. In addition, a polyol having three or more hydroxyl groups and a polyvalent carboxylic acid having three or more carboxyl groups can also be used in combination.

[0027] When the polyester polyol is a dehydration condensate of a cyclic ester such as a lactone, examples thereof include condensates such as ε-caprolactone, γ-valerolactone, α-acetolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone.

[0028] Examples of the polyether polyol include polymers or copolymers of ethylene oxide, propylene oxide, tetrahydrofuran, etc. (i.e., polyethylene glycol, polypropylene glycol, polytetramethylene glycol or copolymers thereof) polyether polyols. Among them, polytetramethylene glycol, polypropylene glycol, and polyethylene glycol are preferred, and the number average molecular weight is preferably 200 to 7,000.

[0029] The polycarbonate polyol is preferably a polycarbonate diol. Moreover, it is still more preferably an aliphatic polycarbonate polyol. The polycarbonate polyol preferably has a number average molecular weight of 500 to 5,000, still more preferably 800 to 4,000, and even more preferably 1,000 to 3,000. The aliphatic polycarbonate polyol is preferably an aliphatic polycarbonate polyol containing a structural unit derived from an aliphatic diol (substituted or unsubstituted alkylene glycol). The aliphatic polycarbonate polyol is not limited by the production method. For example, it is preferably a polycondensate obtained by a transesterification reaction between a substituted or unsubstituted alkylene diol (which may be abbreviated as "alkylene glycol" or "aliphatic diol") and a carbonate compound.

[0030] The alkylene glycol is preferably composed of those having 4 to 10 carbon atoms. For example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butynediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, diethylene glycol, polypropylene glycol, dipropylene glycol, etc. are suitable, and these can be used alone or in admixture of two or more. The substituent of the alkylene glycol is preferably an alkyl group having 10 or less carbon atoms.

[0031] The carbonate compound is not particularly limited, and examples thereof include dialkyl carbonate, diaryl carbonate, or alkylene carbonate. Specific examples of the carbonate compound include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diaryl carbonates such as diphenyl carbonate, and alkylene carbonates such as ethylene carbonate. Since it becomes a polycondensate in the transesterification reaction with a substituted or unsubstituted alkylene glycol and is substituted, the structure of the carbonate compound is not limited, and those having good reactivity may be appropriately selected.

[0032] The above polycarbonate polyol is preferably liquid at 25°C. By using a liquid polycarbonate polyol as a raw material for the polyurethane resin, the flexibility and elasticity of the printed coating film can be ensured, so that the adhesion of the organic solvent-based printing ink to the plastic substrate is improved, and the retort suitability and blocking resistance are improved. For example, an aliphatic polycarbonate diol using an alkylene glycol having an odd number of carbon atoms and a linear structure as the alkylene glycol component and an alkylene glycol having an even number of carbon atoms and a linear structure (linear diol), or an aliphatic polycarbonate polyol using an alkylene glycol having an alkyl substituent (branched diol) is preferably used.

[0033] The aliphatic polycarbonate polyol preferably contains a structural unit derived from a branched diol having a tertiary carbon as the alkylene glycol component. This is because the desorbability and blocking resistance are improved. Examples of the branched diol having a tertiary carbon include 1,2-propanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, etc. Among them, 3-methyl-1,5-pentanediol is preferable. It is preferable to use a linear diol and a branched diol having a tertiary carbon in combination. The mass ratio (the former: the latter) in the total mass of the aliphatic polycarbonate polyol is preferably 70:30 to 5:95, and more preferably 50:50 to 10:90. As the alkylene glycol, 1,6-hexanediol is preferable, and an aliphatic polycarbonate polyol using 1,6-hexanediol and 3-methyl-1,5-pentanediol is more preferable.

[0034] Each type of urethane resin has various properties such as printability and durability. Which choice is the best should be determined in view of the required performance in its end use and cannot be specified generally. However, regardless of which urethane resin is used, the printability, substrate adhesion, adhesive adhesion, and blocking resistance, which are the problems in the present invention, can be sufficiently improved.

[0035] The urethane resin preferably has active hydrogen groups such as hydroxyl groups and / or amino groups in order to obtain adhesion to the substrate or the adhesive. Also, a reaction site with the isocyanate-based curing agent described later can be obtained. The hydroxyl value is preferably 0.5 to 30 mgKOH / g, more preferably 1 to 20 mgKOH / g, and even more preferably 2 to 15 mgKOH / g. The amine value is preferably 0.1 to 15 mgKOH / g, and still preferably 1 to 12 mgKOH / g. On the other hand, the acid value of the urethane resin is preferably 5 mgKOH / g or less, and still preferably 3 mgKOH / g or less. This is because the acid group is hardly reactive with the isocyanate-based curing agent described later.

[0036] The mass average molecular weight of the urethane resin is preferably 5,000 to 300,000, still preferably 7,000 to 150,000, and even more preferably 10,000 to 100,000. When the urethane resin has the above mass average molecular weight, the adhesion between the primer composition and the substrate, and the adhesion between the primer composition and the adhesive become good, and the laminate strength between the substrate and the adhesive becomes practically sufficient.

[0037] Incidentally, the weight average molecular weight of the present invention can be measured by gel permeation chromatography (GPC). As an example, Water 2690 (manufactured by Waters), HLC-8220 (manufactured by Tosoh Corporation) can be used as the GPC device, and PLgel, 5 μm, MIXED-D (manufactured by Polymer Laboratories), TSKgel Super AW series (manufactured by Tosoh Corporation), etc. can be used as the column. As the developing solvent, tetrahydrofuran, 1,2,4-trichlorobenzene, N,N-dimethylformamide (added with 0.01N lithium bromide), etc. can be used, and the flow rate is preferably 0.5 to 1.5 milliliters per minute. For detection, an RI detector or the like can be used, and the measurement can be carried out under conditions such as a sample injection concentration of 0.5 to 1.5 milligrams per milliliter and an injection volume of 0.1 to 1.0 microliters. The weight average molecular weight can be determined as a polystyrene equivalent value.

[0038] The urethane resin may be a urethane resin obtained by blending a polyol and a polyisocyanate in the primer composition and reacting them in the primer layer after printing to generate urethane groups, and the same effect as the above urethane resin appears. As the polyol described above, acrylic polyol, polyester polyol, etc. are suitable, and acrylic polyol is more preferable. As the polyisocyanate, those similar to the polyisocyanate-based curing agent described later are preferable.

[0039] <Vinyl chloride copolymer resin> The primer composition of the present invention preferably further contains a vinyl chloride copolymer resin. Preferred vinyl chloride copolymer resins include vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-acrylic copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, and the like. The mass average molecular weight of the vinyl chloride copolymer resin is preferably from 5,000 to 100,000, more preferably from 5,000 to 50,000. The content of the structural unit derived from the vinyl acetate monomer in 100% by mass of the solid content of the vinyl chloride copolymer resin is preferably from 70 to 95% by mass. Further, the glass transition temperature of the vinyl chloride copolymer resin is preferably from 50°C to 90°C. Further, the vinyl chloride copolymer resin preferably has a hydroxyl group, and the hydroxyl value is preferably from 10 to 200 mgKOH / g. This is because the reactivity with the isocyanate-based curing agent is improved, and the hydroxyl group preferably derives from a hydroxyl group in a vinyl alcohol unit or an acrylic monomer having a hydroxyl group.

[0040] <Cellulose acetate resin> Examples of the cellulose acetate resin include cellulose acetate, cellulose acetate alkylate, and the like. Among them, cellulose acetate alklyates such as cellulose acetate propionate and cellulose acetate butyrate are preferred. Cellulose acetate butyrate is more preferred. The above cellulose acetate resin can be used alone or in combination of two or more. The number average molecular weight of the cellulose acetate resin is preferably from 5,000 to 200,000, more preferably from 10,000 to 100,000, and still more preferably from 15,000 to 65,000. The glass transition point of the cellulose resin is preferably from 100°C to 180°C, more preferably from 120 to 160°C. By using the above urethane resin and cellulose acetate resin in combination, printability, blocking resistance, and the like are improved. Of the total mass of the resin components contained in the primer composition, the content of the cellulose acetate resin is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 5 to 20% by mass. The mass ratio of the urethane resin to the cellulose acetate resin is preferably 100:1 to 100:50, more preferably 100:3 to 100:30, and still more preferably 100:10 to 100:20.

[0041] (Cellulose acetate alkynate) Cellulose acetate alkynate is obtained by reacting cellulose with a suitable organic acid and acid anhydride. That is, cellulose is mixed with a suitable organic acid, acid anhydride, and catalyst and reacted until a triester is formed. After complete triesterification, it is hydrolyzed to achieve the desired level of hydroxyl groups. Cellulose acetate is obtained by triesterifying with acetic acid and then hydrolyzing. Cellulose acetate alkynate preferably has an acetylation degree of 39 to 61% by mass and a hydroxyl group ratio of 0.5 to 3.5% by mass. Cellulose acetate propionate is obtained by triesterifying with acetic acid and propionic acid and then hydrolyzing. Generally, it preferably has an acetylation degree of 0.6 to 2.5% by mass, a propionation degree of 42 to 46% by mass, and a hydroxyl group ratio of 1.8 to 5.0% by mass. Cellulose acetate butyrate is obtained by triesterifying with acetic acid and butyric acid and then hydrolyzing. Generally, it preferably has an acetylation degree of 2.0 to 30.0% by mass, a butyrylation degree of 17 to 53% by mass, and a hydroxyl group ratio of 0.8 to 4.8% by mass.

[0042] <Particles, wax, and other additives> The primer composition of the present invention preferably further contains particles. By containing particles, printability, blocking resistance, and adhesive adhesion are improved. It is also preferable to contain wax. By containing wax, printability and blocking resistance are improved.

[0043] <Particles> Examples of the fine particles used in the present invention include inorganic fine particles such as silicon dioxide, silicate, zeolite, mica, alumina, talc, titanium oxide, iron oxide, zinc oxide, magnesium oxide, calcium carbonate, barium sulfate, and clay, and organic fine particles such as resin beads. It is preferable to use silicon dioxide (silica) which is an inorganic fine particle. By using silica, printability, blocking resistance, and adhesion to the adhesive due to the anchor effect are improved. As the silica, amorphous silica is preferable, but those having shapes such as spherical, scaly, or needle-like, or those supported on other materials such as organic beads can also be used. As the silica, wet silica such as precipitation method and gel method, and dry silica are preferable, and sufficient effects can be obtained with any type. In addition, those hydrophobically treated on the surface with silanes, silicones, fluorines, or those surface-treated with waxes, various surfactants, inorganic salts, etc. are also available, and any of them can be used.

[0044] Specific examples of silica include Nip Gel AZ220 (untreated amorphous silica, particle size 2.6 μm, oil absorption 260 mL / 100 g, manufactured by Tosoh Silica Corporation), Silicia 435 (inorganic-treated amorphous silica, particle size 4.1 μm, oil absorption 220 mL / 100 g, manufactured by Fuji Silicia Co., Ltd.), Mizukasil P526 (untreated amorphous silica, particle size 7 μm, oil absorption 240 mL / 100 g, manufactured by Mizusawa Chemical Industry Co., Ltd.), Syloid ED30 (organically treated amorphous silica, particle size 5 μm, oil absorption 300 mL / 100 g, manufactured by Grace Japan Co., Ltd.), etc.

[0045] From the viewpoints of printability, blocking resistance, and adhesion of the adhesive, the blending amount of the fine particles in the primer composition is preferably 0 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 10 to 30% by mass in the total solid content of the primer composition. The weight ratio of the solid content is preferably 100:0 to 100:50, more preferably 100:5 to 100:30, and still more preferably 100:9 to 100:25. From the same perspective, the particle size of the inorganic fine particles is preferably from 0.1 to 20 μm, more preferably from 0.5 to 15 μm, and particularly preferably from 1 to 11 μm. Further, the oil absorption amount is preferably from 0 to 500 mL / 100 g, more preferably from 90 to 350 mL / 100 g, and particularly preferably from 150 to 330 mL / 100 g.

[0046] <Wax> Examples of the wax used in the present invention include low-density polyethylene wax, high-density polyethylene wax, oxidized polyethylene wax, modified polypropylene wax, fatty acid amide, montan wax, carnauba wax, paraffin wax, microcrystalline wax, ethylene methacrylic acid copolymer wax, vinyl ether wax, shellac wax, Fischer-Tropsch wax, Teflon wax, etc. Among them, it is preferable to use fatty acid amide. By using fatty acid amide, the printing suitability and blocking resistance are improved without impairing the adhesiveness of the adhesive. From the viewpoints of printing suitability and blocking resistance, in the total mass of the primer composition, the blending amount of the wax is preferably from 0 to 20% by mass in terms of solid content, more preferably from 3 to 18% by mass, and particularly preferably from 5 to 15% by mass.

[0047] Specific examples of the wax include Amide P (fatty acid amide, manufactured by Kao Corporation), Luwax A Powder (low-density polyethylene wax, manufactured by BASF Japan Ltd.), Hiwax 320MP (low-density polyethylene wax, manufactured by Mitsui Chemicals, Inc.), MP-28 (high-density polyethylene wax, manufactured by Micropulders, etc.

[0048] From the viewpoint of achieving the effects of the present invention, the viscosity of the primer composition of the present invention is preferably from 1 to 10,000 mPa·s, more preferably from 10 to 1,000 mPa·s. Within the above viscosity range, the printing reproducibility is improved. The viscosity represents a value obtained by the method described in JIS Z8803:2011 and is a measured value at 25°C using a B-type viscometer.

[0049] <Hardening agent> The primer composition of the present invention can use a polyisocyanate-based hardening agent as the hardening agent. The hardening agent is not particularly limited as long as it contains a group having reactivity with the hydroxyl group in the polyol main agent. As the isocyanate compound, a urethane prepolymer which is a diisocyanate or a reaction product of a diisocyanate and a polyol is preferable, and as such a diisocyanate, various known aromatic, aliphatic or alicyclic diisocyanates can be used. For example, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylenediisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, m-tetramethylxylylene diisocyanate, and dimer diisocyanate obtained by converting the carboxyl group of dimer acid into an isocyanate group can be mentioned. These can be used alone or in combination of two or more. Among these, from the viewpoints of preventing yellowing and imparting flexibility for improving adhesion, the use of aliphatic diisocyanates such as hexamethylene diisocyanate and xylylene diisocyanate, and alicyclic diisocyanates such as isophorone diisocyanate is preferable, and from the viewpoint of compatibility with retort resistance, it is preferable to use it as a polyisocyanate compound having three or more functional groups such as an adduct body such as trimethylolpropane, an isocyanurate body, or a burette body.

[0050] As one embodiment, the ratio NCO / OH of the hydroxyl group of the polyol to the isocyanate group of the isocyanate compound is preferably 1.0 to 8.0, and more preferably 1.5 to 5.0. As one embodiment, the mass ratio of the curing agent to the urethane resin or polyol is preferably 100:0 to 100:40, more preferably 100:5 to 100:30, and still more preferably 100:10 to 100:25.

[0051] <Medium> The primer composition of the present invention may contain an organic solvent, water, or other liquid media. Although not limited, examples of suitable organic solvents include toluene and other aromatic organic solvents, methyl ethyl ketone and other ketone organic solvents, ethyl acetate, normal propyl acetate and other ester organic solvents, ethanol, isopropanol, normal propanol and other alcohol organic solvents. The liquid medium may contain water, and when the organic solvent is the main medium, the water content is preferably 10% by mass or less.

[0052] <Substrate> The base material used in the present invention is mainly in the form of a film or a sheet. There is no limitation on the material constituting the base material, but a resin base material (plastic base material) is preferred. Examples of the type of resin constituting the resin base material include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polylactic acid, polycarbonate resin, acrylic resins such as polymethyl methacrylate, polyamide resins such as 6-nylon and 6,6-nylon, cellulose resins such as cellulose acetate, cellulose propionate, and nitrocellulose, chlorinated polyolefin resins such as polyvinyl chloride and polyvinylidene chloride, fluorinated polyolefin resins such as polytetrafluoroethylene and polyvinylidene fluoride, polystyrene resin, AS resin, ABS resin, etc. It is preferably obtained by using a mixture selected from one or more of these thermoplastic resins. Further, a surface treatment such as corona treatment may be performed, or a colored base material in which a colorant is kneaded into the above thermoplastic resin may be used. The colorant is not particularly limited, and known organic pigments, inorganic pigments, etc. can be appropriately used.

[0053] <Adhesive layer> The adhesive layer is formed by an adhesive and is for adhering the base material and the decorative substrate (decorative material substrate). The adhesive is selected according to the material of the decorative substrate, and known adhesives can be used. For example, urethane resin adhesives, urea resin adhesives, melamine resin adhesives, phenol resin adhesives, resorcinol resin adhesives, aqueous polymer-isocyanate adhesives, vinyl acetate resin emulsion adhesives, chloroprene rubber adhesives, epoxy resin adhesives, modified silicone adhesives, hot melt adhesives, dry laminate adhesives, etc. can be mentioned.

[0054] Conditions such as the drying temperature and drying time of the adhesive are not particularly limited and may be appropriately set according to the type of the adhesive. The coating method of the adhesive is not particularly limited, and for example, methods such as roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating, blade coating, smooth coating, comma coating, etc. can be adopted.

[0055] <Decorative substrate> As the decorative substrate, various wood materials, metal materials, plastic materials, ceramic materials, etc. are used. Specifically, wood veneers, plywood, particle boards, medium density fiberboards (MDF), wood fiberboards, laminated woods, etc. made of various trees such as cedar, pine, cypress, oak, lauan, teak, merapi, etc., metals such as iron and aluminum, resins such as acrylic, polycarbonate, ethylene-vinyl acetate copolymer, ethylene vinyl acetate, polyester, polystyrene, polyolefin, ABS, phenolic resin, cellulose-based resin, rubber, etc. Flat plates, curved plates, etc. made of plates, sheets (or films), or various three-dimensional shaped articles (molded products) are targeted.

[0056] <Decorative material> The primer composition of the present invention is used to form the primer layer of a decorative material having a base material, a primer layer, and an adhesive layer in sequence. Further, a printing layer formed by printing ink or a surface protection layer may be provided on a surface different from the primer layer with respect to the base material. That is, as an example of the embodiment of the present invention, the following examples can be cited. Surface protection layer / Printing layer / Base material / Primer layer / Adhesive layer / Decorative substrate

[0057] <Printing> The primer composition of the present invention can be printed by any printing method without any particular limitation. Among them, the printing method in gravure printing can be preferably used.

[0058] <Gravure printing> (Gravure plate) In the above gravure printing, the gravure plate is a cylindrical one made of metal, and recesses are created in various colors by engraving or etching / laser. As the number of lines, those with 75 lines to 250 lines are appropriately used. As the thickness of the primer layer, 0.1 μm to 100 μm is preferable, and 0.5 μm to 5 μm is more preferable.

[0059] (Printing press) In a gravure printing machine, one printing unit is equipped with the above-mentioned gravure plate and doctor blade. There are multiple printing units, and printing units corresponding to printing inks can be set, and each unit has an oven drying unit. Printing is performed by rotation and is a roll-fed printing method. The type of plate and the type of doctor blade can be appropriately selected, and those corresponding to the specifications can be selected.

Example

[0060] More specific embodiments of the present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. Also, unless otherwise specified, in the examples and comparative examples, "parts" and "%" represent "parts by mass" and "mass %", respectively.

[0061] (Hydroxyl value) The hydroxyl value was measured based on the method specified in JIS K0070 (1992).

[0062] (Amine value) The amine value was measured by the following method. A sample was accurately weighed at 0.5 - 2 g (sample amount: S g). 30 mL of neutral ethanol (BDG neutral) was added to the accurately weighed sample and dissolved. The resulting solution was titrated with a 0.2 mol / L ethanolic hydrochloric acid solution (titre: f). The point at which the color of the solution changed from green to yellow was taken as the end point, and the amine value was determined based on the following (Equation 2) from the titration volume (A mL) at this time. (Equation 2) Amine value = (A × f × 0.2 × 56.108) / S

[0063] (Weight-average molecular weight (Mw)) Mw was measured using a GPC (gel permeation chromatography) apparatus ("Shodex GPC System-21" manufactured by Showa Denko KK) to measure the molecular weight distribution, and was determined as the polystyrene-equivalent molecular weight. The measurement conditions are shown below. Column: A plurality of the following columns were connected in series and used. TSKgel Super AW2500, manufactured by Tosoh Corporation, TSKgel Super AW3000, manufactured by Tosoh Corporation, Manufactured by Tosoh Corporation, TSKgel Super AW4000, Manufactured by Tosoh Corporation, TSKgel guard column Super AW H Detector: RI (Differential Refractometer) Measurement conditions: Column temperature 40 °C, Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min

[0064] (Synthesis Example 1) [Synthesis of Urethane Resin A1] Using the synthesis conditions of polyurethane resin PU2 in JP-A-2018-53014, a polyester-based urethane resin A1 with a solid content of 30%, an amine value of 8.2 mg KOH / g, a hydroxyl value of 2.4 mg KOH / g, and a weight average molecular weight of 42,000 was obtained.

[0065] (Synthesis Example 2) [Synthesis of Urethane Resin A2] Using the synthesis conditions of polyurethane resin PU1 in JP-A-2019-112583, a polyester-based urethane resin A2 with a solid content of 30%, an amine value of 7.0 mg KOH / g, a hydroxyl value of 22.1 mg KOH / g, and a weight average molecular weight of 40,000 was obtained.

[0066] (Synthesis Example 3) [Synthesis of Urethane Resin A3] Using the synthesis conditions of polyurethane resin PU1 in JP-A-2018-53014, a polyether-based urethane resin A3 with a solid content of 30%, an amine value of 9.5 mg KOH / g, a hydroxyl value of 7.3 mg KOH / g, and a weight average molecular weight of 40,000 was obtained.

[0067] (Synthesis Example 4) [Synthesis of Urethane Resin A4] Using the synthesis conditions of polyurethane resin P1 in JP-A-2020-169280, a polycarbonate-based urethane resin A4 with a solid content of 30%, an acid value of 35 mg KOH / g, and a weight average molecular weight of 35,000 was obtained.

[0068] (Preparation of Hardener) 40 parts of Duranate 24A-100 (HDI-based polyisocyanate, manufactured by Asahi Kasei Corporation), 10 parts of Takenate D-140N (IPDI-based polyisocyanate, manufactured by Mitsui Chemicals, Inc.), and 50 parts of ethyl acetate were thoroughly stirred and mixed to obtain an isocyanate-based curing agent C1 solution (solid content 67.5%, NCO group content 15.2%). 40 parts of Vasonate HB100 (HDI-based polyisocyanate, manufactured by BASF Japan Ltd.), 30 parts of Takenate D-110N (XDI-based polyisocyanate, manufactured by Mitsui Chemicals, Inc.), and 30 parts of ethyl acetate were thoroughly stirred and mixed to obtain an isocyanate-based curing agent C2 solution (solid content 62.5%, NCO group content 12.3%).

[0069] (Example 1) [Preparation of Primer Composition S1] 40 parts of polyester-based urethane resin A1, 3 parts of vinyl chloride copolymer resin A7 (Solvay TA5R, vinyl chloride-vinyl acetate-alcohol copolymer, hydroxyl value 146 mgKOH / g, Mn 28000, Tg 78 °C, manufactured by Shin-Etsu Chemical Co., Ltd.), and cellulose acetate-based resin A10 (CAB381-0.1, cellulose acetate butyrate resin, Mn 20000, Tg 121 °C, manufactured by Eastman Chemical Company) were mixed and heated and dissolved at 40 °C for 2 hours. 5 parts of inorganic particles B1 (Nipgel AY220, silica, manufactured by Tosoh Silica Corporation, average particle size 2.5 μm, oil absorption 260 ml / 100 g) and 3 parts of wax B4 (fatty acid amide P, fatty acid amide, manufactured by Kao Corporation) were added and stirred with a blade mixer for 1 hour. 3 parts of curing agent C1, 14 parts of methyl ethyl ketone (hereinafter also referred to as MEK), 11 parts of isopropyl alcohol (hereinafter also referred to as IPA), and ethyl acetate were added to a total of 100 parts as a primer composition, and the whole was stirred with a blade mixer so that all became uniform to obtain primer composition S1.

[0070] (Examples 2 to 24) [Preparation of Primer Compositions S2 to S24] Primer compositions S2 to S24 were obtained in the same manner as in Example 1, except that the raw materials and formulations described in Table 1 were changed. In the table, numerical values without unit markings represent parts, and blank spaces indicate non-formulation. The abbreviations in the table are as follows. · Acrylic polyol resin A5 (Acrit 6AN-3000, acrylic polyol resin, solid content 37.5%, Tg 100 °C, acid value 3.5 mg KOH / g, hydroxyl value 15 mg KOH / g, manufactured by Daisei Fine Co., Ltd.) · Polyester resin A6 (Vylon 200, polyester resin, solid content 100%, Tg 67 °C, acid value 2 mg KOH / g, hydroxyl value 6 mg KOH / g, manufactured by Toyobo Co., Ltd.) · Vinyl chloride copolymer resin A8 (Solvay CH, vinyl chloride-vinyl acetate copolymer, Mn 50000, Tg 70 °C, manufactured by Shin-Etsu Chemical Co., Ltd.) · Vinyl chloride copolymer resin A9 (Vinol E15 / 40A, vinyl chloride-acrylic copolymer, Mn 45000, Tg 69 °C, manufactured by Wacker) · Cellulose acetate resin A11 (CAB381-20, cellulose acetate butyrate resin, Mn 70000, Tg 141 °C, manufactured by Eastman Chemical Co., Ltd.) · Cellulose acetate resin A12 (CAB553-0.4, cellulose acetate butyrate resin, Mn 20000, Tg 136 °C, manufactured by Eastman Chemical Co., Ltd.) · Cellulose acetate resin A13 (CAB171-15, cellulose acetate butyrate resin, Mn 65000, Tg 161 °C, manufactured by Eastman Chemical Co., Ltd.) · Cellulose acetate resin A14 (CAB482-0.5, cellulose acetate propionate resin, Mn 25000, Tg 142 °C, manufactured by Eastman Chemical Co., Ltd.) · Cellulose acetate resin A15 (CA398-3, cellulose acetate resin, Mn 30000, Tg 180 °C, manufactured by Eastman Chemical Co., Ltd.) · Inorganic fine particles B2 (Silicia 435, inorganic-treated amorphous silica, particle size 4.1 μm, oil absorption 220 mL / 100 g, manufactured by Fuji Silicia Co., Ltd.) Inorganic fine particles B3 (Tospearl 145, silicone resin beads, particle size 4.5 μm, oil absorption ml / 100 g, manufactured by Momentive Performance Materials, Inc.)

[0071] (Comparative Examples 1 to 4) [Preparation of Primer Compositions T1 to T4] Primer compositions T1 to T4 were obtained in the same manner as in Example 1, except that the raw materials and compositions were changed as shown in Table 2. In the table, values ​​without units indicate parts, and blanks indicate that no compound was added. The abbreviations in the table are as follows. Nitrocellulose resin A16 (DHX40-70, nitrocellulose, manufactured by Inabata & Co., Ltd.)

[0072] [Performance evaluation] (Printability (coating film removal on guide roll)) Each primer composition was applied onto a PET substrate (E5200, biaxially oriented polyethylene terephthalate film, 25 μm) using a wire bar (manufactured by Matsuo Sangyo Co., Ltd.). It was then dried in an electric oven at 40°C for 10 seconds, and the coating amount was 1 g / m 2 Printed matter G1a to G24a (Examples) and H1a to H4a (Comparative Examples) were obtained. The coating amount was adjusted by adding additional ethyl acetate solvent or by changing the size of the wire bar. Cover the printed matter with aluminum foil and apply 1N / cm to an area of ​​4cm x 4cm from the aluminum foil side. 2 A load of 10 ... Score 5: No peel resistance at all. Rating 4: There is slight resistance, but no migration of the primer layer. Rating 3: Heavy resistance but no migration of the primer layer. Score 2: Heavy resistance and migration of the primer layer. Rating 1: There is heavy resistance and the substrate or aluminum foil is damaged. A rating of 3 or above is considered to be at a practical level.

[0073] (Adhesion to substrate) PET substrate (E5200, biaxially stretched polyethylene terephthalate film, 25 μm), olefin substrate (FOR, biaxially stretched polypropylene film, 30 μm thick, manufactured by Futamura Chemical Co., Ltd.), polyvinyl chloride substrate (semi-rigid polyvinyl chloride film, 80 μm thick), each primer composition was applied to each with a wire bar (manufactured by Matsuo Sangyo Co., Ltd.), dried in an electric oven at 40 °C for 30 seconds, and the coating amount after drying was 1 g / m 2 Each printed matter was obtained, and by storing it in an electric oven (40 °C, non-humidified) for 3 days, G1a~24a (PET substrate examples) and H1a~H4a (PET substrate comparative examples), G1b~G24b (olefin substrate examples) and H1b~H4b (olefin substrate comparative examples), G1c~G24c (polyvinyl chloride substrate examples) and H1c~H4c (polyvinyl chloride substrate comparative examples) of printed matters were obtained. The printed matters were evaluated in five grades by the cross-cut test of JIS K5600 "General Test Methods for Paints". Score 5: No peeling at all. Score 4: Peeling with an area greater than 0% and within 10%. Score 3: Peeling with an area greater than 10% and within 25%. Score 2: Peeling with an area greater than 25% and within 75%. Score 1: Peeling with an area greater than 75%. Note that a score of 3 or more is a practical and usable level.

[0074] (Adhesive adhesion) Using the printed matters G1b~G24b and H1b~H4b obtained under the same conditions as the above substrate adhesion test and Adhesive 1 (Hybon 486S, reactive PUR adhesive, manufactured by Hitachi Chemical Co., Ltd.), Adhesive 1 was applied to a decorative substrate (medium density fiberboard) with a solid content coating thickness of 40 μm, and each printed matter was pasted at 55 °C, and stored under a pressure of 1 N / cm in a 23 °C environment 2 for 24 hours to obtain laminates I1~I22 (examples) and J1~J4 (comparative examples). Similarly, using Adhesive 2 (Deer Brand PIBOND 2300, aqueous polymer isocyanate type, manufactured by Oshika Corporation), K1~K22 (examples) and L1~L4 (comparative examples) were obtained. The printed matter on the laminate was peeled at a speed of 200 m / min at an angle of 180°, and the state after peeling was evaluated in five grades. Score 5: The substrate stretches or breaks without peeling. Or the decorative substrate breaks. Score 4: The printed matter peels off and the adhesive layer breaks. Score 3: The printed matter peels off and peels at the adhesive layer / primer layer or primer layer / substrate layer with an area of less than 25%. Score 2: The printed matter peels off and peels at the adhesive layer / primer layer or primer layer / substrate layer with an area of 25% or more and less than 50%. Score 1: The printed matter peels off and peels at the adhesive layer / primer layer or primer layer / substrate layer with an area of 50% or more. Note that a score of 3 or more is a practical and usable level.

[0075] (Blocking resistance) In the printed matters G1b to 24b (olefin substrate examples) and H1b to 4b (olefin substrate comparative examples) of the olefin substrate prepared under the same conditions as the above substrate adhesion test, the printing layer was applied to the surface different from the primer layer on the substrate with a wire bar (manufactured by Matsuo Sangyo Co., Ltd.) to obtain the front and back coated products. The printing layer could be applied under the same conditions as LP Bio SXR39 blue (manufactured by Toyo Ink Co., Ltd.) for the primer layer. Prepare two of the above front and back coated products and stack them so that the primer layer surface and the printing layer surface are in contact. Apply a load of 50 N / cm 2 to an area of 4 cm x 4 cm and store it under the conditions of 40°C and 80% RH. After 24 hours, peel off the stacked front and back coated products, and evaluate the peel resistance and the degree of ink transfer in five grades. Score 5: There is no peel resistance and no transfer of the printing layer. Score 4: There is a slight resistance but no transfer of the printing layer. Score 3: There is a heavy resistance but no transfer of the printing layer. Score 2: There is a heavy resistance and partial transfer of the ink layer. Score 1: There is a heavy resistance and the entire ink layer transfers. Note that a score of 3 or more is a practical and usable level.

[0076] (Adhesive adhesion over time) After storing the laminates I1 to I24 (Examples) and J1 to J4 (Comparative Examples) used in the evaluation of the adhesive adhesion at 40°C for one month, the same evaluation as for the adhesive adhesion was performed. Score 5: The substrate stretches or breaks without peeling. Or the decorative substrate breaks. Score 4: The printed matter peels off and the adhesive layer breaks. Score 3: The printed matter peels off and peels at the adhesive layer / primer layer or primer layer / substrate layer with an area of less than 25%. Score 2: The printed matter peels off and peels at the adhesive layer / primer layer or primer layer / substrate layer with an area of 25% or more and less than 50%. Score 1: The printed matter peels off and peels at the adhesive layer / primer layer or primer layer / substrate layer with an area of 50% or more. In addition, a score of 3 or more is a practical and usable level.

[0077] [Table 1]

[0078] [Table 2]

Claims

1. A primer composition for forming the primer layer of a decorative material having a substrate, a primer layer, and an adhesive layer in contact with the primer layer in sequence, The primer composition contains a urethane resin and a cellulose acetate resin.

2. The primer composition according to claim 1, wherein the cellulose acetate resin is cellulose acetate propionate and / or cellulose acetate butyrate.

3. The primer composition according to claim 1 or 2, wherein the urethane resin contains at least one selected from the group consisting of polyester-based urethane resins, polyether-based urethane resins, acrylic-based urethane resins, and polycarbonate-based urethane resins.

4. The primer composition according to claim 1 or 2, further containing a vinyl chloride copolymer resin.

5. The primer composition according to claim 1 or 2, further containing fine particles.

6. The primer composition according to claim 5, wherein the fine particles are silica.

7. The primer composition according to claim 1 or 2, further containing wax.

8. A method for manufacturing a decorative material having a substrate, a primer layer, and an adhesive layer in sequence, Including step (1) of applying a primer composition on the substrate to form a primer layer, and step (2) of applying an adhesive on the primer layer to form the adhesive layer, The method for manufacturing a decorative material, wherein the primer composition contains a urethane resin and a cellulose acetate resin.

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