JP4629352B2 - Aqueous coating solution for adhesive layer, laminate and method for producing laminate - Google Patents

Description

  The present invention relates to an aqueous coating solution for an adhesive layer, a laminate having an adhesive layer formed with the aqueous coating solution for an adhesive layer, and a method for producing the laminate, and more specifically, an adhesive layer having sufficient adhesive strength. A water-based coating solution for an adhesive layer which can be formed and has a long pot life and excellent environmental safety, a laminate having a sufficient adhesive force and a good design formed by this coating solution, and such a laminate The present invention relates to a method for manufacturing a body.

  The aqueous coating solution for the adhesive layer usually contains a resin, a cross-linking agent and a solvent as main components, but the adhesive layer formed from such an aqueous coating solution for the adhesive layer is applied with the aqueous coating solution for the adhesive layer. After drying, it is adjusted so as to have a predetermined adhesive property by applying a curing treatment for promoting a crosslinking reaction.

  The combination of the resin and the crosslinking agent contained in the adhesive layer aqueous coating solution is roughly classified into a combination in which a crosslinking reaction proceeds in a low temperature region and a combination in which a crosslinking reaction proceeds in a high temperature region. Among these, the adhesive layer formed with the aqueous coating solution for an adhesive layer that undergoes a crosslinking reaction mainly in a low temperature region undergoes a crosslinking reaction by a curing treatment (also referred to as aging) in a low temperature region (about 5 to 40 ° C.). It has the advantage of proceeding and exhibiting sufficient adhesive properties. In addition, the water-based coating liquid for the adhesive layer in which the crosslinking reaction hardly proceeds in the low temperature region (about 5 to 40 ° C.) and the crosslinking reaction proceeds mainly in the high temperature region (about 70 to 180 ° C.) has a long pot life. There is an advantage that the stability of the liquid is excellent.

  By the way, as a laminated body which has the adhesive layer formed in part from such an adhesive coating liquid, what laminated | stacked the base material, the adhesive layer, and the resin layer (base material) one by one is known.

  However, the adhesive layer aqueous coating solution that undergoes a crosslinking reaction in the low-temperature region described above easily reacts with the main agent and / or solvent, and is poor in stability of the adhesive layer aqueous coating solution itself (pot life is shortened). When such an aqueous coating liquid for adhesive layers is used in the production of a laminate, there is a problem that it is difficult to form a layer having a stable and sufficient adhesive strength.

  On the other hand, when a laminate is produced by melt extrusion coating a resin layer on an adhesive layer formed using the aqueous coating liquid for an adhesive layer that undergoes a crosslinking reaction in the high temperature region described above, the crosslinking reaction is melted. When proceeding with heat at the time of extrusion, there is almost no deterioration in the design of the laminate, but because melt extrusion coating is performed in a short time, depending only on the heat at the time of melt extrusion coating There was a problem that the cross-linking reaction could not proceed sufficiently, and a laminate having poor interlayer adhesion between the substrate and the resin layer was formed.

  Moreover, the laminated body (refer FIG. 1) which has the adhesive layer formed partially using the aqueous | water-based coating liquid for adhesive layers in which a crosslinking reaction hardly progresses in a low temperature area | region and a crosslinking reaction advances in a high temperature area | region was mentioned above. When exposed to a high temperature region, the base material contracts, resulting in a problem that dimensional stability is lowered or design properties are lowered. In addition, even in a laminate (see FIG. 2) in which a pattern coloring layer is provided between a base material and an adhesive layer, the pattern is distorted by exposure to the above-described high temperature region, resulting in a decrease in design properties. There was a problem to do.

  The present invention has been made to solve the above-described problems, and its object is to provide an aqueous coating solution for an adhesive layer that can form an adhesive layer having sufficient adhesive force and has a long pot life. Another object of the present invention is to provide a laminate having a sufficient adhesive force and good design formed by this coating liquid, and to provide a method for producing such a laminate.

  The adhesive layer aqueous coating solution of the present invention that solves the above problems is an adhesive layer aqueous coating solution that undergoes a crosslinking reaction in two different temperature ranges, and includes two types of crosslinking agents corresponding to the crosslinking reaction, and It is characterized by containing a resin corresponding to the crosslinking agent. More specifically, the aqueous coating liquid for an adhesive layer of the present invention comprises a crosslinking agent a that causes a crosslinking reaction at least in a low temperature region, a resin A having a functional group that reacts with at least the crosslinking agent a, and the low temperature region. It is characterized in that it contains at least a crosslinking agent b that causes a crosslinking reaction in a high temperature region and a resin B having a functional group that reacts with the crosslinking agent b.

  According to the present invention, since the crosslinking reaction can occur in two different temperature regions, the crosslinking reaction can be caused stepwise in the case of passing through a process in which different temperatures are applied. For example, when the coated adhesive layer passes through a high temperature atmosphere and a low temperature atmosphere, the crosslinking agent b and the resin B cause a crosslinking reaction in the high temperature atmosphere (and in some cases, the crosslinking agent a and the resin A also cause a crosslinking reaction). ) In a low temperature atmosphere, the crosslinking agent a and the resin A cause a crosslinking reaction, and an adhesive layer having a sufficient adhesive force is formed. Furthermore, this aqueous coating liquid for adhesive layer comprises a crosslinking reaction necessary for having sufficient adhesive force, and a crosslinking agent b and a resin A, which are excellent in stability. And the stability of the aqueous coating liquid for the adhesive layer is further improved.

  In the aqueous coating solution for an adhesive layer of the present invention, the resin A and the resin B are the same compound, and the compound has a functional group that reacts with the crosslinking agent a and a functional group that reacts with the crosslinking agent b. Is preferred. In the aqueous coating solution for an adhesive layer of the present invention, the crosslinking agent a is preferably an isocyanate group-containing compound, the resin A is preferably a resin having a hydroxyl group, and the crosslinking agent b is It is an epoxy group-containing compound, and the resin B is preferably a resin having a carboxyl group. Furthermore, in the aqueous coating solution for an adhesive layer of the present invention, the low temperature region is preferably in the range of 5 ° C to 40 ° C, and the high temperature region is preferably in the range of 70 ° C to 180 ° C.

  The laminate of the present invention that solves the above problems is a laminate in which a base material, an adhesive layer, and a resin layer are laminated in this order, and the adhesive layer has a crosslinking agent a that causes a crosslinking reaction at least in a low temperature region, and At least a resin A having a functional group that reacts with the cross-linking agent a, a cross-linking agent b that hardly undergoes a cross-linking reaction in the low-temperature region and a cross-linking reaction in a high-temperature region, and at least a functional group that reacts with the cross-linking agent b It is characterized by being formed with an aqueous coating solution for an adhesive layer containing resin B.

  According to this invention, the adhesive layer contains the crosslinking agent a that causes a crosslinking reaction at least in the low temperature region and the resin A, and the crosslinking agent b that causes little crosslinking reaction in the low temperature region and a resin B that causes the crosslinking reaction in the high temperature region. Since the adhesive layer undergoes a high-temperature atmosphere and a low-temperature atmosphere, the crosslinking agent b and the resin B undergo a crosslinking reaction in the high-temperature atmosphere. a and the resin A also cause a crosslinking reaction), and the crosslinking agent a and the resin A cause a crosslinking reaction in a low temperature atmosphere. Such an adhesive layer causes a cross-linking reaction in two different temperature regions, and thus has sufficient adhesive force. As a result, a laminate having high interlayer adhesion between the substrate and the resin layer is obtained. Furthermore, since the cross-linking reaction occurs in two temperature regions, a high temperature region and a low temperature region, there is an effect that it is possible to suppress a decrease in design properties of the laminate by adjusting the time of exposure to a high temperature atmosphere.

  In addition, as a specific structure of the laminated body, the base material is a thermoplastic resin made of a polyolefin-based resin, a colored layer is formed between the base material and the adhesive layer, and a decoration process is performed. Form a concavo-convex pattern on the surface side, form a partially colored layer on the concave portion of the concavo-convex pattern, form a protective layer on the outermost surface of the resin layer, or form a primer layer on the back surface of the substrate be able to.

  The manufacturing method of the laminated body of the present invention that solves the above-mentioned problems involves applying an aqueous coating liquid for an adhesive layer on a substrate to form an adhesive layer, and melt extruding the resin for the resin layer on the adhesive layer. A method for producing a laminate in which a resin layer is formed and then cured in a predetermined low temperature region, wherein the adhesive coating aqueous coating solution includes a crosslinking agent a that causes a crosslinking reaction at least in a low temperature region, and at least the crosslinking A resin A having a functional group that reacts with the agent a, a cross-linking agent b that hardly undergoes a cross-linking reaction in the low temperature region and a cross-linking reaction in the high temperature region, and a resin B having a functional group that reacts with at least the cross-linking agent b The adhesive layer is characterized by being formed by causing a crosslinking reaction in a high temperature region during the melt extrusion and causing a crosslinking reaction in a low temperature region during the curing treatment.

  According to this invention, the adhesive layer formed on the substrate is exposed to a high-temperature atmosphere when the resin layer is melt-extruded, whereby the crosslinking agent b and the resin B in the adhesive layer cause a crosslinking reaction ( In some cases, the cross-linking agent a and the resin A also undergo a cross-linking reaction). Thereafter, the cross-linking agent a and the resin A in the adhesive layer cause a cross-linking reaction by being exposed to a low temperature atmosphere during the curing treatment. In such a laminate, an adhesive layer having sufficient adhesive strength is formed by the aqueous coating liquid for the adhesive layer that causes a crosslinking reaction in two different temperature regions, so that the interlayer adhesion between the base material and the resin layer is improved. High laminates are produced. Furthermore, since the cross-linking reaction takes place in two temperature regions, a high temperature region and a low temperature region, it is difficult to cause distortion and shrinkage by adjusting the exposure time to a high temperature atmosphere for a short time. There is an effect that it is possible to suppress the deterioration of the design property of the.

  In the manufacturing method of the laminated body of this invention, it is preferable that the said curing process is hold | maintained in the said low-temperature area | region using oven. Thus, the curing treatment can be performed while maintaining a constant temperature by using the oven.

  According to the aqueous coating solution for an adhesive layer of the present invention, the crosslinking reaction between the resin and the crosslinking agent proceeds sufficiently at low and high temperatures, so that an adhesive layer having sufficient adhesive force can be formed. Moreover, since it is not necessary to perform the curing treatment at a high temperature for a long time, problems such as the occurrence of distortion due to the curing temperature do not occur. In addition, since the component that reacts with the solvent can be reduced among the resin component and the crosslinking agent component, the stability of the aqueous coating liquid for the adhesive layer is not lowered, and an adhesive layer having stable adhesive properties is formed. be able to.

  In the laminate of the present invention and the production method thereof, the resin layer is formed by the melt extrusion coating method on the adhesive layer formed using the aqueous coating liquid for the adhesive layer of the present invention. Due to the heat applied to the layer, a crosslinking reaction Q based on the crosslinking agent b occurs, and then a crosslinking reaction P based on the crosslinking agent a occurs by performing a curing treatment at room temperature (about 25 ° C.). The laminate of the present invention thus produced can improve interlayer adhesion between the base material and the resin layer by the action of the formed adhesive layer. Furthermore, since the laminate of the present invention is not subjected to a long-term curing treatment at a high temperature, there is no problem of distortion or shrinkage, and a laminate excellent in design can be produced.

  Hereinafter, an aqueous coating solution for an adhesive layer, a laminate, and a method for producing the laminate of the present invention will be described with reference to the drawings.

(1) Aqueous Coating Solution for Adhesive Layer The aqueous coating solution for an adhesive layer of the present invention is a coating solution that causes a crosslinking reaction in two different temperature ranges, and includes two types of crosslinking agents corresponding to the crosslinking reaction, and A resin corresponding to the crosslinking agent is contained. The cross-linking reaction that occurs in two different temperature regions here is a cross-linking reaction P that occurs at least in the low temperature region, and a cross-linking reaction Q that hardly occurs in the low temperature region and occurs in the high temperature region.

  The aqueous coating solution for adhesive layer of the present invention contains an aqueous resin and an aqueous crosslinking agent. That is, in the present invention, the water-based resin and / or the water-based cross-linking agent is essentially a water-soluble resin and / or a cross-linking agent, a water-soluble treated resin and / or a cross-linking agent, and essentially water-dispersible. Resin and / or crosslinking agent, water-dispersed resin and / or crosslinking agent.

Crosslinking reaction P: The crosslinking reaction P proceeds at a temperature range of low temperature of at least 5 to 40 ° C., but may proceed at a temperature range exceeding that temperature range as long as the temperature range is included. The cross-linking agent a that causes the cross-linking reaction P in such a temperature range and the resin A corresponding to the cross-linking agent a are, for example, a combination of the cross-linking agent a and the resin A that proceeds in a low temperature range of at least 5 to 40 ° C. The crosslinking reaction may proceed in a high temperature region described later.

  Examples of combinations of groups having reactivity between the crosslinking agent a and the resin A include, for example, isocyanate groups and hydroxyl groups, isocyanate groups and amino groups, amino groups and cyclocarbonate groups, aziridine groups and carboxyl groups, carbodiimide groups and carboxyl groups. And a combination of an amino group and an epoxy group, a silanol group and a hydroxyl group, and the like. In such a combination of the crosslinking agent a and the resin A, the crosslinking reaction P can be caused in the temperature range of 5 to 40 ° C. as described above.

  In particular, the combination of the crosslinking agent a and the resin A is preferably a combination of the crosslinking agent a which is an isocyanate group-containing compound and the resin A having a hydroxyl group as a reactive group. Specifically, this combination includes a combination of an isocyanate cross-linking agent a containing an isocyanurate bond, a polyurethane resin A having a hydroxyl group, a polyester resin A having a hydroxyl group, and / or an acrylic resin A having a hydroxyl group. Preferably mentioned.

Crosslinking reaction Q: The crosslinking reaction Q is a reaction that hardly occurs in a low temperature region of 5 to 40 ° C. and proceeds in a high temperature region of 70 to 180 ° C. The crosslinking agent b causing the crosslinking reaction Q in such a high temperature region and the resin B corresponding to the crosslinking agent b are, for example, a combination of the crosslinking agent b and the resin B in which the crosslinking reaction Q proceeds exclusively in a high temperature region of 70 to 180 ° C. I just need it.

  Examples of such a combination of the crosslinking agent b and the resin B include an epoxy group and a carboxyl group, an oxazoline group and a carboxyl group, and a carboxyl group and a hydroxyl group.

  In particular, the combination of the crosslinking agent b and the resin B is preferably a combination of the crosslinking agent b that is a compound having an epoxy group and the resin B that is a compound having a carboxyl group. Specifically, as this combination, a glycidyl ether type epoxy crosslinking agent having a sorbitol skeleton and / or a glycidyl ether type epoxy crosslinking agent having a glycerol skeleton, a urethane resin having a carboxyl group, and a carboxyl group. A combination with a polyester resin and / or a resin B which is an acrylic resin having a carboxyl group is preferred.

  In addition, the resin (A, B) described above may be a mixture of three or more kinds of resins (A, B) as long as the resin (A, B) corresponds to each cross-linking agent (a, b).

  On the other hand, the resin A and the resin B can be made the same compound as long as they correspond to the respective crosslinking agents (a, b) and can cause a crosslinking reaction in the two different temperature ranges described above. In this case, the compound needs to have both a functional group that reacts with the crosslinking agent a and a functional group that reacts with the crosslinking agent b. For example, an isocyanate group-containing compound is included as a crosslinking agent a that causes a crosslinking reaction P in a low temperature region of at least 5 to 40 ° C., and hardly occurs in a low temperature region of 5 to 40 ° C., and a crosslinking reaction occurs in a high temperature region of 70 to 180 ° C. An epoxy group-containing compound is contained as the crosslinking agent b that causes Q, and the resin (A, B) that undergoes a crosslinking reaction at each temperature with these two types of crosslinking agents (a, b) contains a hydroxyl group and a carboxyl group. An aqueous coating solution for an adhesive layer containing one kind of resin can be used.

Solvent; The solvent is contained in the aqueous coating liquid for the adhesive layer in order to dissolve or disperse the crosslinking agent and the resin. As the solvent, water or a mixed solvent composed of water and alcohols is used. The water used as the solvent is industrial water of a grade conventionally used for aqueous coating solutions. In addition, when using a mixed solvent composed of water and alcohol, the alcohol constituting the mixed solvent includes lower alcohols such as methanol, ethanol, isopropyl alcohol and n-propyl alcohol, glycols and esters thereof, and the like. Can be mentioned. These solvents, such as lower alcohols, glycols and esters thereof, are used for the purpose of improving the fluidity of aqueous coating liquids, improving the wetness of the coated body, and adjusting the drying properties. The type, amount used, etc. are determined according to the purpose.

  In a mixed solvent composed of water and alcohol, the blending ratio thereof can be adjusted in the range of water: alcohol etc. = 100: 0 to 30:70.

Mixing ratio: crosslinking agent A in the adhesive layer aqueous coating liquid of the present invention: The blending ratio of the crosslinking agent B is 20: 80 to 80: 20, preferably 40: 60 to 80: 20. By setting the blending ratio of the crosslinking agents (A, B) within such a range, the crosslinking reaction (P, Q) can be appropriately caused in the two different temperature ranges described above.

  The compounding ratio of resin (A + B): crosslinking agent (a + b) is 25:75 to 90:10, preferably 50:50 to 80:20. By setting the blending ratio of the resin and the crosslinking agent within such a range, the crosslinking reaction (P, Q) can be appropriately caused in the two different temperature ranges described above.

  The ratio of the sum of the resin and the crosslinking agent: solvent is 80:20 to 5:95, preferably 60:40 to 10:90. By setting it within such a range, the crosslinking reaction (P, Q) can be appropriately caused in the two different temperature ranges described above.

Adjustment of adhesive layer aqueous coating liquid and formation of adhesive layer ; adhesive layer aqueous coating liquid includes colorants, waxes, dispersants, antifoaming agents, leveling agents, stabilizers, fillers, lubricants, Additives such as lubricants, light stabilizers, ultraviolet absorbers, antioxidants, fungicides, bactericides, tackifiers and film-forming aids may be optionally added. The aqueous coating solution for an adhesive layer of the present invention is prepared by blending predetermined amounts of various compounds and the like and thoroughly mixing with a mixer or the like.

  The adhesive layer aqueous coating solution thus prepared is coated or printed, and then dried to form an adhesive layer. As coating methods, various known 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, spray coating. It is possible to use a method such as flow coating or brush coating. In addition, as printing methods, various known methods such as relief printing such as gravure, letterpress and flexographic printing, lithographic printing such as lithographic offset and dilitho printing, stencil printing such as silk screen, electrostatic printing and ink jet printing are used. Can do. At this time, it coats so that the film thickness of a contact bonding layer may be set to about 0.5-10 micrometers.

  The adhesive layer after coating and drying is exposed to a predetermined temperature within a high temperature range of 70 to 180 ° C., for example, a temperature of 140 to 160 ° C. for 1 to 30 seconds, whereby the crosslinking agent b and the resin B A crosslinking reaction Q, and thereafter, exposure to a predetermined temperature within a low temperature range of 5 to 40 ° C., for example, a temperature of 20 to 40 ° C. for 3 to 7 days, A crosslinking reaction P occurs with the resin A. The crosslinking reaction P in this low temperature region proceeds by being held at a constant temperature using, for example, an oven. Moreover, since the crosslinking reaction Q in the high temperature region proceeds by being exposed to the above-described temperature, it may be exposed to a higher temperature environment.

  As described above, the aqueous coating liquid for an adhesive layer of the present invention causes a crosslinking reaction in two different temperature ranges, and thus when undergoing a process to which different temperatures are applied, causes a crosslinking reaction in stages. be able to. For example, when the coated adhesive layer passes through a high temperature atmosphere and a low temperature atmosphere, the crosslinking agent b and the resin B cause a crosslinking reaction in the high temperature atmosphere (and in some cases, the crosslinking agent a and the resin A also cause a crosslinking reaction). ) In a low temperature atmosphere, the crosslinking agent a and the resin A cause a crosslinking reaction, and an adhesive layer having a sufficient adhesive force is formed. Furthermore, since the aqueous coating solution for adhesive layer contains the crosslinking agent b and resin B excellent in stability, the stability of the entire aqueous coating solution for adhesive layer is further improved.

(2) Laminated body and its manufacturing method As shown in FIGS. 1-3, the laminated body of this invention is the laminated body 1, 101, 111 which laminated | stacked the base material 2, the contact bonding layer 3, and the resin layer 4 in this order. (Hereinafter, abbreviated as “laminated body 1” unless otherwise specified.) The adhesive layer 3 has a crosslinking agent a and a resin A that cause a crosslinking reaction at least in a low temperature region, and almost a crosslinking reaction in the low temperature region. It is formed with an aqueous coating liquid for an adhesive layer containing a crosslinking agent b and a resin B that cause a crosslinking reaction in a high temperature region without causing the above.

  As a specific configuration of the laminate 1 of the present invention, the base material 2 is made of a thermoplastic resin made of a polyolefin resin, or a colored layer 11 is formed between the base material 2 and the adhesive layer 3 to decorate the base material 2. Or forming a concavo-convex pattern 7 on the surface side of the resin layer 4, forming a partially colored layer 8 in a recessed portion of the concavo-convex pattern 7, or forming a protective layer 9 on the outermost surface of the resin layer 4. The primer layer 10 can be formed on the back surface of the substrate 2.

(Base material)
The base material 2 is an essential configuration in the laminate 1, and various olefin-based resins shown below can be preferably applied. For example, (a) a mixture having high-density polyethylene or polypropylene as a hard segment and an elastomer or inorganic filler as a soft segment, (b) JP-A-9-1111055, JP-A-5-77371, An ethylene-propylene-butene copolymer described in Kaihei 7-316358 and the like, (c) an isotactic polypropylene as a hard segment and an attack as a soft segment described in JP-B-6-23278 A mixture with tic polypropylene can be used.

  The high-density polyethylene as the hard segment (a) is preferably a polyethylene having a specific gravity of 0.94 to 0.96, which has a high degree of crystallinity obtained by the low-pressure method and has few branched structures in the molecule. High-density polyethylene which is a polymer is used. As the polypropylene as the hard segment, isotactic polypropylene is preferably used.

  Diene rubber, hydrogenated diene rubber, olefin elastomer, and the like are used as the elastomer (i) as the soft segment. The hydrogenated diene rubber is obtained by adding a hydrogen atom to at least a part of the double bond of the diene rubber molecule, and suppresses the crystallization of the polyolefin resin to improve its flexibility. . Examples of the diene rubber include isoprene rubber, butadiene rubber, butyl rubber, propylene / butadiene rubber, acrylonitrile / butadiene rubber, acrylonitrile / isoprene rubber, and styrene butadiene rubber. The olefin elastomer is an elastic copolymer to which at least one polyene copolymerizable with two or more olefins is added. Ethylene, propylene, α-olefin, etc. are used as the olefin, 1,4 hexadiene, cyclic diene, norbornene and the like are used. Preferred examples of the olefin elastomer include elastic copolymers containing olefin as a main component such as ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene rubber, and ethylene-butadiene copolymer rubber. Note that these elastomers may be overcrosslinked using a crosslinking agent such as an organic peroxide or sulfur as necessary.

  The amount of these elastomers added is 10 to 60% by weight, preferably about 30% by weight. If the amount of elastomer added is less than 10% by weight, the change in the constant load elongation becomes too steep, and the elongation at break, impact resistance, and easy adhesion are reduced. When the added amount of the elastomer is higher than 60% by weight, transparency, weather resistance and creep resistance are deteriorated.

  As the inorganic filler (a), powder having an average particle size of about 0.1 to 10 μm, such as calcium carbonate, barium sulfate, clay, and talc, is used. As addition amount, it is 1 to 60 weight%, Preferably it is 5 to 30 weight%. When the added amount of the inorganic filler is less than 1% by weight, the creep deformation resistance and the easy adhesion property are lowered. Moreover, when the addition amount of an inorganic filler exceeds 60 weight%, the elongation at break and impact resistance will fall.

  As the (olefin) olefin resin, a thermoplastic elastomer made of an ethylene / propylene / butene copolymer resin is used. Here, as butene, any of the three structural isomers of 1 butene, 2 butene, and isobutylene can be used. The copolymer is a random copolymer and includes a part of an amorphous part.

  Preferable specific examples of the ethylene / propylene / butene copolymer resin include the following (a) to (c).

  (A) A random copolymer made of a terpolymer of ethylene, propylene and butene described in JP-A-9-1111055. In this random copolymer, the weight ratio of the propylene component is preferably 90% by weight or more, and the melt flow rate is 1 to 50 g / 10 min under the conditions of 230 ° C. and 2.16 kg. preferable. Such a random copolymer comprises 0.01 to 50 parts by weight of a transparent nucleating agent mainly composed of a phosphoric acid aryl ester compound and a fatty acid amide having 12 to 22 carbon atoms with respect to 100 parts by weight of the random copolymer. 0.003 to 0.3 parts by weight is melt kneaded.

  (B) A terpolymer of ethylene, propylene and butene described in JP-A-5-77371. This copolymer is obtained by adding 80 to 0% by weight of crystalline polypropylene to 20 to 100% by weight of an amorphous polymer having a propylene component weight ratio of 50% by weight or more.

  (C) A terpolymer of ethylene, propylene and 1-butene described in JP-A-7-316358. In this copolymer, propylene and / or 1 butene content was mixed with 20 to 100% by weight of a low crystalline polymer having a content of 50% by weight or more and 80 to 0% by weight of a crystalline polyolefin such as isotactic polypropylene. An oil gelling agent such as N acylamino acid amine salt and N acylamino acid ester is added in an amount of 0.5% by weight to the composition.

  The ethylene / propylene / butene copolymer resins of the above (a) to (c) may be used alone, or may be further mixed with other polyolefin resins as necessary.

  As the olefin-based resin (c), as described in Japanese Patent Publication No. 6-23278, the (A) soft segment has a number average molecular weight Mn of 25000 or more, and a weight average molecular weight Mw and a number average molecular weight Mn. 10% to 90% by weight of atactic polypropylene soluble in boiling heptane with a ratio Mw / Mn ≦ 7, and (B) as a hard segment, an isotactic insoluble in boiling heptane having a melt index of 0.1 to 4 g / 10 min. Examples thereof include soft polypropylene composed of a mixture of 90 to 10% by weight of tic polypropylene.

  Among the olefinic thermoplastic elastomers (c) above, those composed of a mixture of isotactic polypropylene and atactic polypropylene and having a weight ratio of 5 to 50% by weight of atactic polypropylene are preferably used. Those having a weight ratio of 20 to 40% by weight are particularly preferably used. When the weight ratio of the atactic polypropylene is less than 5% by weight, when embossing or forming into an article having a three-dimensional shape or a concavo-convex shape, deformation of the non-uniform sheet-like substrate due to necking may occur. As a result, wrinkles, pattern distortion, etc. occur. On the other hand, when the weight ratio of the atactic polypropylene exceeds 50% by weight, the sheet-like base material itself is easily deformed, and the base material is deformed when the base material is passed through a printing machine, and the pattern of the colored layer 11 is distorted. In addition, defects such as misregistration are likely to occur in the case of multicolor printing, and the sheet is easily torn during molding.

  A colorant, a heat stabilizer, a flame retardant, an ultraviolet absorber, a radical scavenger, and the like are added to the above-described olefin resin forming the substrate 2 as necessary.

  Coloring agents include titanium white, zinc white, red bean, vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, carbon black and other inorganic pigments, isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, etc. Organic pigments or dyes, metallic pigments made of foil powder such as aluminum and brass, pearlescent pigments made of foil powder such as titanium dioxide-coated mica and basic zinc carbonate, and the like are used. Moreover, you may add an inorganic filler in the ratio of 5 to 60 weight% as needed. Examples of the inorganic filler include powders of calcium carbonate, barium sulfate, clay, talc, silica (silicon dioxide), alumina (aluminum oxide), and the like. The colorant is added to give the base material 2 the necessary color as the laminate 1 and may be either transparent coloring or opaque (concealing) coloring, but generally in order to conceal the adherend. Opaque coloring is preferred.

  As the heat stabilizer, known ones such as phenol, sulfite, phenylalkane, phosphite, and amine can be used, and the prevention of deterioration such as thermal discoloration during heat processing can be improved. A flame retardant is added when imparting flame retardancy, and powders such as aluminum hydroxide and magnesium hydroxide are used. The ultraviolet absorber is for imparting better weather resistance (light resistance) to the resin, and is an organic substance such as benzotriazole, benzophenone, salicylic acid ester, or particulate zinc oxide having a diameter of 0.2 μm or less, Inorganic substances such as cerium oxide and titanium oxide are used. In addition, a reactive ultraviolet absorber in which an acryloyl group or a methacryloyl group is introduced into the benzotriazole skeleton is also used. In addition, the addition amount of these ultraviolet absorbers is about 0.5 to 10 weight% normally. The radical scavenger is for further preventing deterioration due to ultraviolet rays and improving weather resistance, and includes bis- (2,2,6,6-tetramethyl-4-biperidinyl) sebacate and bis- (N-methyl). -2,2,6,6-tetramethyl-4-biperidinyl) sebacate, and other hindered radical scavengers such as compounds disclosed in JP-B-4-82625, biperidinyl radical scavengers, etc. Is done.

  The base material 2 can be obtained by forming a film obtained by arbitrarily selecting and blending the above materials by a conventional method such as calendering. The thickness of the base material 2 is 50-200 micrometers, Preferably it is about 100 micrometers.

  The surface of the substrate 2 on the surface side (resin layer 4 side) of the laminate 1 is preferably subjected to easy adhesion treatment such as application of an easy adhesion layer, corona discharge treatment, plasma treatment, and ozone treatment. Examples of the resin constituting the easy adhesion layer (also referred to as a primer layer or an anchor layer) include (meth) acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester resin, urethane resin, chlorinated polypropylene, and polyethylene chloride. .

  In addition to the base material 2 composed of the above-described polyolefin resin, a woven or non-woven fabric using an organic resin such as polyester or vinylon, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer , Vinyl resins such as ethylene-vinyl alcohol copolymer, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, (meth) acrylic resins such as polymethyl methacrylate, polymethyl acrylate and polyethyl methacrylate, polystyrene, acrylonitrile A sheet or film made of a resin such as butadiene-styrene copolymer (ABS), cellulose triacetate, cellophane, or polycarbonate can be used as the substrate 2. In addition, thin paper, kraft paper, titanium paper, linter paper, paperboard, gypsum board paper, fine paper, coated paper, art paper, sulfuric acid paper, glassine paper, parchment paper, paraffin paper, etc. A so-called vinyl wallpaper original fabric obtained by sol coating or dry laminating vinyl can also be used. Further, a sheet or film made of inorganic fibers such as glass fibers, asbestos, potassium titanate fibers, alumina fibers, silica fibers, and carbon fibers can be used as the substrate 2. Moreover, metal foils, such as aluminum, iron, stainless steel, copper, etc. can also be used. Further, a material obtained by laminating a plurality of such base material materials can be used as the base material 2.

(Colored layer)
The colored layer 11 is an arbitrary layer in the laminate 1 and is composed of the solid colored layer 5 and / or the pattern colored layer 6.

  As shown in FIG. 2, the solid colored layer 5 is provided for the purpose of concealing the background of the substrate 2, and is usually formed as a solid solid colored layer having no pattern. On the other hand, the pattern coloring layer 6 has a pattern or color consisting of a wood grain pattern, a stone pattern, a cloth pattern, a leather pattern, a geometric figure, etc., depending on figures, characters, symbols, colors, combinations thereof, etc. On the colored layer 5, it is formed as a planar, uneven, or convex (see FIG. 2) layer. In addition, the pattern coloring layer 6 may also serve as the solid coloring layer 5. In this case, the pattern coloring layer 6 becomes the solid coloring layer 5. The solid colored layer 5 and / or the pattern colored layer 6 thus formed may be provided on the entire surface of the substrate 2 or may be partially provided. Further, as shown in FIG. 2, the colored layer 11 is composed of a solid colored layer 5 provided on the entire surface of the substrate 2 and a pattern colored layer 6 provided partially on the surface of the solid colored layer 5. You can also.

  The main component of the aqueous coating liquid for the adhesive layer described above used for the adhesive layer 3 can be used as the main component of the coating liquid for the colored layer.

  Examples of the color layer coating liquid include, for example, a urethane resin-based water-based color coating liquid, a polyester resin-based water-based color coating liquid, an acrylic resin-based water-based color coating liquid, and an acrylic nitrified cotton-based water-based color coating liquid. Liquid, polyvinyl alcohol-based aqueous coloring coating liquid, casein-based aqueous coloring coating liquid, cellulose-based aqueous coloring coating liquid, and starch-based aqueous coloring coating liquid.

  When the colored layer 11 is formed with the aqueous coating solution for an adhesive layer of the present invention, it is possible to further improve the adhesive properties and the design properties, which is a preferred embodiment. In addition, when the colored layer 11 is formed with the aqueous coating solution for an adhesive layer of the present invention, the operational effect is the same as the operational effect exhibited by the adhesive layer 3 formed with the aqueous coating solution for an adhesive layer described later. .

  Organic or inorganic pigments can be used as the color pigments contained in the various colored layer coating liquids described above. For example, as yellow pigments, azo pigments such as monoazo, disazo and polyazo, organic pigments such as isoindolinone, inorganic pigments such as yellow lead, yellow iron oxide, cadmium yellow, titanium yellow and antimony yellow can be used. it can. As the red pigment, azo pigments such as monoazo, disazo and polyazo, organic pigments such as quinacridone, and inorganic pigments such as petals, vermilion, cadmium red and chrome vermilion can be used. As the blue pigment, organic pigments such as phthalocyanine blue and indanthrene blue, and inorganic pigments such as bitumen, ultramarine blue, and cobalt blue can be used. Moreover, as a black pigment, organic pigments, such as aniline black, and inorganic pigments, such as carbon black, can be used. As the white pigment, inorganic pigments such as titanium dioxide, zinc white, and antimony trioxide can be used. Moreover, fillers, such as a silica, volume pigments, such as an organic bead, a neutralizing agent, surfactant, etc. can be contained arbitrarily.

  The colored layer coating liquid used for the solid colored layer 5 and the pattern colored layer 6 is a wax, a dispersant, an antifoaming agent, a leveling agent, a stabilizer, a filler, depending on the type of the coating liquid. Lubricants, lubricants, and other additives are optionally added and prepared by mixing thoroughly with a mixer or the like.

  The solid colored layer 5 and the pattern colored layer 6 are formed by applying the above-described various colored layer coating liquids by coating or printing, and then drying. More specifically, the solid colored layer 5 is usually formed by applying or printing a solid colored layer coating solution, followed by drying and curing. The pattern coloring layer 6 is also formed by applying or printing a pattern coloring layer coating solution, followed by drying and curing. As coating methods, various known 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, spray coating. It is possible to use a method such as flow coating or brush coating. In addition, as printing methods, various known methods such as relief printing such as gravure, letterpress and flexographic printing, lithographic printing such as lithographic offset and dilitho printing, stencil printing such as silk screen, electrostatic printing and ink jet printing are used. Can do. The solid colored layer 5 is coated or printed so that the film thickness after drying is about 0.5 to 5 μm, and the pattern colored layer 6 is such that the film thickness after drying is about 0 to 5 μm. Coated or printed.

(Adhesive layer)
The adhesive layer 3 is a layer formed with the above-described aqueous coating liquid for adhesive layer of the present invention, and is an essential component for the laminate 1 of the present invention. As shown in FIGS. 1 to 3, the adhesive layer 3 is provided between the base material 2 and the resin layer 4 and improves the adhesion between the base material 2 and the resin layer 4. And has the effect of improving durability and long-term appearance maintenance. Moreover, when the colored layer 11 which consists of the solid colored layer 5 and / or the pattern colored layer 6 is formed on the base material, by forming the adhesive layer 3 on the colored layer 11, the base material 2 / The adhesion between the colored layer 11 and the resin layer 4 can be improved, and the pattern can be maintained for a long time.

  The adhesive layer 3 is as described in detail in the above-mentioned aqueous coating liquid for adhesive layer, and a resin A having a cross-linking agent a that causes a cross-linking reaction at least in a low-temperature region and a functional group that reacts with at least the cross-linking agent a. A water-based coating liquid for an adhesive layer, which comprises: a crosslinking agent b that hardly undergoes a crosslinking reaction in the low-temperature region and a crosslinking reaction that causes a crosslinking reaction in a high-temperature region; and a resin B having a functional group that reacts with at least the crosslinking agent b Formed with.

  The adhesive layer 3 is formed by applying or printing the above-described aqueous coating liquid for adhesive layer of the present invention, and then drying to form an adhesive layer. As coating methods, various known 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, spray coating. It is possible to use a method such as flow coating or brush coating. In addition, as printing methods, various known methods such as relief printing such as gravure, letterpress and flexographic printing, lithographic printing such as lithographic offset and dilitho printing, stencil printing such as silk screen, electrostatic printing and ink jet printing are used. Can do. At this time, it coats so that the film thickness of a contact bonding layer may be set to about 0.5-10 micrometers.

  For example, the adhesive layer after coating and drying is crosslinked by being exposed to a predetermined temperature within a high temperature range of 70 to 180 ° C., for example, a temperature of 140 to 160 ° C. for 1 to 30 seconds. By causing a crosslinking reaction Q between the agent b and the resin B, and then exposing to a predetermined temperature within the range of 5 to 40 ° C., for example, a temperature of 20 to 40 ° C. for 3 to 7 days The crosslinking reaction P is caused between the crosslinking agent a and the resin A.

  The cross-linking reaction P in the low temperature region proceeds by being held at a constant temperature using, for example, an oven. Further, since the crosslinking reaction Q in the high temperature region proceeds by being exposed to the above-described temperature, when the resin material in the molten state described later is extrusion coated onto the adhesive layer 3, it is exposed to a higher temperature environment. It may be done.

  In the adhesive layer 3, the crosslinking agent b and the resin B undergo a crosslinking reaction in a high temperature atmosphere (and the crosslinking agent a and the resin A also undergo a crosslinking reaction in some cases), and the crosslinking agent a and the resin A undergo a crosslinking reaction in a low temperature atmosphere. Therefore, an adhesive layer having a sufficient adhesive force is formed. This is because the crosslinking agent B advances the crosslinking reaction by heat when the resin layer 4 described later is formed by melt extrusion coating, and further the curing temperature is set to room temperature (about 25 ° C.). By allowing the crosslinking reaction to proceed. In addition, since most of the cross-linking reaction is performed in a low temperature region, when the pattern colored layer 6 is provided, the pattern is not distorted and the base material does not shrink, and as a result, the design of the laminate does not occur. There is no advantage. In addition, you may perform the curing process in this low-temperature area | region using oven.

(Resin layer)
The resin layer 4 is also referred to as a top resin layer, and is an adhesive layer for the purpose of protecting the base material 2 and the colored layer 11 from scratches, improving the surface strength of the laminate 1, and imparting a feeling of painting. 3 on the base material 2 or the colored layer 11. The resin layer 4 is also an essential configuration for the laminate 1 of the present invention.

  The resin layer 4 is formed on the adhesive layer 3 by a melt extrusion coating method. As the resin formed by the melt extrusion coating method, a thermoplastic resin is used, and in particular, a thermoplastic resin formed with good adhesion on the substrate 2 or the colored layer 11 through the adhesive layer 3 is preferably used. For example, polyolefin resin, polyester resin, acrylic resin, and the like can be given. Among these, as the polyolefin-based resin, for example, one or two or more mixed resins such as polypropylene, ethylene / butene copolymer, low-density polyethylene, and cyclic polyolefin-based resin are used. The resin material forming the resin layer 4 is added with known additives such as a colorant, a filler, an ultraviolet absorber, a light stabilizer, an antioxidant, and a matting agent as necessary.

  In the melt extrusion coating method, the above-mentioned resin material is heated to a molten state, and the molten resin is extruded from a T die of an extruder onto a substrate to be coated (in the present invention, an adhesive layer). Thereafter, the resin layer is formed on the coated substrate by pressurizing and cooling the coated layer and the coated substrate between the rollers. Other known methods can be used for the extrusion method and cooling method in this melt extrusion coating method, and other known methods can also be used for the die and the cooler. At this time, the thickness of the resin layer 4 is applied so as to be about 3 to 200 μm.

  In the present invention, immediately before the molten resin material is extrusion coated on the adhesive layer 3, the resin material is air-cooled to some extent and reaches a predetermined temperature (eg, 140 to 160 ° C.) between 70 and 180 ° C. And the adhesive layer 3 are pressurized and cooled between rollers, and the adhesive layer 3 and the resin layer 4 are laminated.

  By melt extrusion coating of the resin layer 4 at such a temperature, the crosslinking reaction Q of the adhesive layer 3 that is the substrate to be coated can be caused. As described above, the adhesive layer after coating / drying is exposed to a predetermined temperature within a range of 70 to 180 ° C. for 1 to 30 seconds, so that the crosslinking layer b and the resin B are exposed to each other. Since the crosslinking reaction Q is caused, the crosslinking reaction Q can be caused by exposure to a temperature of 140 to 160 ° C. for several seconds in the melt extrusion coating.

  In addition, as shown in FIG. 3, you may make a resin layer into the multilayer structure of two or more layers by the melt coextrusion coating method. At this time, the resin layer 14 composed of two or more layers may be melt-extruded and applied via an adhesive layer that acts as a primer layer or an anchor layer.

  The resin layer 14 formed by laminating two or more layers is advantageous in that the resin layer 4 ′ on the substrate 2 side and the resin layer 4 ″ on the protective layer 9 side can have different functions and effects. As a specific example, the resin layer 4 ″ on the protective layer 9 side is formed of a resin mainly composed of a fluorine-based resin such as vinylidene fluoride, and imparts excellent surface functions such as stain resistance. The resin layer 4 ′ on the side can be formed of a thermoplastic acrylic resin or the like to improve the adhesion between the adhesive layer 3 and the like.

(Uneven pattern)
The uneven pattern 7 is also referred to as an embossed pattern, and is formed on the surface of the resin layer 4 as necessary, as shown in FIG. Further, when two or more resin layers 14 are formed as shown in FIG. 3, the concavo-convex pattern 7 is formed on the outermost resin layer 4 ″ or formed on the resin layer 4 ′ other than the outermost surface. can do.

  The uneven pattern 7 is not particularly limited as long as it is a pattern according to the use of the laminate 1. For example, wood grain conduit groove, wood ring annual unevenness, floated annual ring uneven surface, wood surface uneven surface, sand texture, pear texture, hairline, line-shaped groove, granite cleaved surface texture, textured surface texture, skin squeezing, text, geometry Examples include academic patterns.

  Examples of means for forming the concavo-convex pattern 7 include an embossing method by heat and pressure and a T-die melt extrusion method. The embossing method by heating and pressurizing is a method in which the surface of the resin layer 4 is heated and softened, the surface is pressed with an embossing plate to form an uneven pattern 7 on the embossing plate, and cooled and fixed. Single-wafer or rotary embossing machines are used. When the resin layer 4 is laminated by the T-die melt extrusion method, a cooling roller that also serves as a shaping roller is used, and the uneven pattern 7 is formed simultaneously with the formation and lamination of the resin layer 4. The embossed pattern can also be formed by hairline processing, sandblasting, or the like.

  In addition, when the heat at the time of embossing can raise | generate a crosslinking reaction, the crosslinking reaction Q can also be advanced with the heat at the time of embossing.

(Partial colored layer)
The partially colored layer 8 is formed in the recessed portion 17 of the concavo-convex pattern 7 by a wiping method. In the wiping method, the coating liquid for the partially colored layer is applied to the entire surface including the recessed portion 17 by the doctor blade coating method or the knife coating method, and then the coating solution for the partially colored layer is applied from the surface other than the recessed portion 17. This is a method of forming the partially colored layer 8 only in the recessed portion 17 by removing the same. As the coating liquid for the partially colored layer, a coating liquid comprising a colored pigment such as an organic pigment, an inorganic pigment, or a bright pigment and a binder resin such as a thermoplastic resin, a thermosetting resin, or an ionizing radiation curable resin. Alternatively, an emulsion-type aqueous coating solution can be used.

(Protective layer)
The protective layer 9 is also referred to as a topcoat layer or an overprint layer (OP layer), and covers the surface of the recessed portion 17 that forms the uneven pattern 7 and the surface of the partially colored layer 8 that is formed in the recessed portion 17. It is provided for the purpose of protecting.

  Since the protective layer 9 is used for the purpose of improving physical properties such as scratch resistance and stain resistance, it is preferable to use a thermosetting resin and / or an ionizing radiation curable resin. Although it may be formed with a solvent-based coating solution, it is desirable to form with a water-based coating solution or a solvent-free coating solution in consideration of environmental safety that suppresses the occurrence of VOC. When a solvent-free coating solution is used, an ionizing radiation curable coating solution is preferred. As an aqueous coating liquid, an aqueous resin is used, and further, a colorant, a dispersant, an antifoaming agent, a leveling agent, a stabilizer, a filler, a lubricant, a lubricant, and other additives are optionally added, and an aqueous solvent. Alternatively, an aqueous coating solution prepared by sufficiently mixing with a mixer or the like using a mixed solvent composed of water and alcohol or the like is preferably used.

  As the ionizing radiation curable resin, a monomer having a radically polymerizable unsaturated group such as (meth) acryloyl group or (meth) acryloyloxy group or a cationically polymerizable functional group such as epoxy group in the molecule, It consists of a polymer or a polymer (hereinafter collectively referred to as a compound). These monomers, prepolymers, and polymers are used alone or in combination. Such an ionizing radiation curable resin is sufficiently cured when irradiated with an electron beam, but when it is cured by irradiation with ultraviolet rays, a photopolymerization initiator is added as a sensitizer. The addition amount of the photopolymerization initiator is generally about 0.1 to 10 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin.

  Moreover, the protective layer 9 can also be formed with a reactive aqueous resin composition, and the scratch resistance and the adhesion to the resin layer 4 can be improved. In particular, when an emulsion type resin is used, a reaction initiator such as a curing agent is protected in the resin composition, and the reaction can be started after coating. Therefore, the protective layer 9 can be formed by coating with a resin composition that is easy to apply and then reacting. As such a reaction type resin composition, for example, as a heat sensitive reaction type resin, so as to suppress a reaction between a resin composed of a resin having an active hydrogen group and an isocyanate group, water of a solvent or an alcohol compound, Hydrophilically treated isocyanate-based curing agent, or resin composition obtained by emulsifying isocyanate-based curing agent treated with a blocking agent, or water-soluble or water having an epoxy group and a resin comprising a resin having an amino group or a carboxylic acid group The resin composition etc. which consist of a dispersible hardening | curing agent can be mentioned.

  The protective layer 9 is provided in order to improve surface properties such as scratch resistance, and the gloss is adjusted by adding a known matting agent such as silica to the coating solution, or the design property such as a feeling of painting. Can be provided. Moreover, in order to provide the protective layer 9 with better weather resistance or light resistance, the layer can be formed using a coating liquid to which an ultraviolet absorber or a light stabilizer is added as necessary. .

  The protective layer 9 is formed by coating and forming the above-described various coating liquids by a known coating method such as a gravure coating method, a reverse roll coating method, a knife coating method, a kiss coating method, or other coating methods. Moreover, it forms by well-known printing methods, such as gravure printing and silk screen printing. The thickness of the formed protective layer 9 is preferably about 0.5 to 40 μm, and more preferably 3 to 10 μm.

(Primer layer)
The primer layer 10 is formed on the back surface side of the base material 2 for the purpose of easily bonding the laminate 1 of the present invention to various adherends. The primer layer 10 is formed using (meth) acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, chlorinated polyethylene, or the like. From the viewpoint of environmental safety, it is preferable to use an aqueous coating solution used for forming No. 3.

(Laminate)
The laminate 1 of the present invention having the above-described configuration can be used for decorative sheets, soft packaging materials, boil packaging materials, and the like.

  When the laminated body 1 is used as a decorative sheet, it is used by being laminated on another adherend (backing material). The adherend is a three-dimensional article, a plate material such as a flat plate or a curved surface, or an article of various shapes such as a sheet (or film). Examples of such adherends include wood veneer, wood plywood, particle board, medium density fiberboard (MDF), etc., wood fiberboard, etc., metal such as iron, aluminum, (meth) acrylic, polyester , Polystyrene, polyolefin, ABS resin, phenol resin, polyvinyl chloride resin, cellulose resin, rubber resin, glass, ceramics such as ceramics, non-cement ceramic materials such as gypsum, fine paper, Japanese paper, carbon Nonwoven fabric or woven fabric made of fibers such as asbestos, potassium titanate, glass, and synthetic resin.

  In the relationship between the laminate 1 and the adherend, if the substrate 1 or the primer layer 10 of the laminate 1 can be directly bonded to the adherend by heat fusion or the like, the laminate 1 and the adherend Can be laminated without using an adhesive, but depending on the type of the substrate 2 or the primer layer 10 of the laminate 1, an appropriate adhesive can be used if it cannot be directly adhered to the adherend by thermal fusion or the like. Are laminated using Examples of the adhesive include vinyl acetate-based and urea-based adhesives.

  Further, as a general lamination method, for example, (a) a method of laminating an adherend with a pressure roller via an adhesive, (b) Japanese Patent Publication No. 50-19132, Japanese Patent Publication No. 43- As described in Japanese Patent No. 27488, etc., a laminating agent is inserted between both male and female molds for injection molding, both molds are closed, molten resin is injected and filled from a male mold gate, and then cooled and resin molded. Simultaneously with the molding of the product, the injection molding simultaneous laminating method in which the decorative sheet 1 is laminated on the surface thereof, (c) as described in JP-B-56-45768, JP-B-60-58014, etc. A vacuum press laminating method in which the laminate 1 is opposed to the surface of the molded article and the laminate 1 is laminated on the molded article surface by a pressure difference caused by vacuum suction from the molded article side, (d) Japanese Patent Publication No. 61-5895, Described in Japanese Patent Publication No. 3-2666 In other words, while supplying the laminated body 1 via an adhesive in the longitudinal direction of a columnar adherend such as a cylinder or a polygonal column, a plurality of rollers constituting different directions are used to form a plurality of side surfaces constituting the columnar adherend. Examples include a lapping process method in which the laminated body 1 is sequentially laminated by pressure bonding.

  Various adherends laminated with decorative sheets, which are the laminate 1 of the present invention, are subjected to a predetermined molding process and used as various decorative materials. For example, interior decorations for buildings such as walls, ceilings, floors, surface decorations for furniture such as window frames, doors, handrails, surface decorations for cabinets for furniture or light electrical / OA equipment, vehicle interiors such as automobiles and trains, aircraft interiors, windows Uses such as glass for cosmetics are listed.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. Here, in this example, a decorative sheet will be described as an application of the aqueous coating solution for an adhesive layer of the present invention, but this does not limit the application of the aqueous coating solution for an adhesive layer of the present invention. . In addition, below, a part is a mass part.

Example 1
A polypropylene-based elastomer colored sheet PB013 (thickness 60 μm) manufactured by Mitsubishi Chemical MKV Co., Ltd. is used as the base material 2, and a corona discharge treatment is performed thereon, and then a gravure plate with a line number of 54 lines / inch and a plate depth of 40 μm is prepared. A solid colored layer aqueous coating solution A and a pattern colored layer aqueous coating solution B having the following composition were sequentially applied and dried by a gravure printing method to obtain a solid colored layer 5 of about 2 μm and a patterned colored layer 6 of about 1 μm. Were sequentially formed.

Furthermore, using a gravure plate having a line number of 54 lines / inch and a plate depth of 40 μm, an aqueous coating solution a for an adhesive layer having the following composition is applied and dried by gravure printing so as to be about 3 g / m ^2. After drying, an adhesive layer 3 having a thickness of 10 μm was formed.

  Furthermore, the adhesive layer 3 is bonded by coextrusion coating of an easily adhesive resin made of ethylene butene copolymer (manufactured by Nippon Synthetic Rubber Co., Ltd., EBM2021P) and a polyolefin resin having the following composition under ozone irradiation. Layer 4 was formed. Specifically, the film thickness ratio of easy-adhesive resin: polyolefin resin is 2: 8 at a temperature of 180 ° C., and is co-extruded onto a sheet in a molten state from a T-die of a co-extruder, and between pressure rollers with a cooling mechanism. The resin layer 4 having a thickness of about 80 μm was formed by applying pressure (pressure 5 to 10 kgf / cm). At this time, the adhesive layer was exposed to a temperature of about 140 to 160 ° C. for about 3 seconds.

  Next, a concavo-convex pattern 7 is formed on the surface of the laminated sheet by embossing at about 150 ° C. for 3 seconds. The protective layer aqueous coating solution C having the following composition was applied and dried by a gravure printing method to form a protective layer 9 of about 4 μm. Then, the decorative sheet of Example 1 was obtained by curing at a temperature of 25 ° C. for 7 days.

Water-based coating liquid A for solid colored layer ;
Aqueous urethane-based white ink (The Inktec, Oude WKE): 100 parts, Water-dispersible isocyanurate bond-containing isocyanate crosslinking agent (Nippon Polyurethane Industry Co., Ltd., AQ100): 10 parts, Water: 20 parts, Isopropyl alcohol : 20 copies
Water-based coating liquid B for pattern coloring layer ;
Aqueous urethane-based yellow ink (Ode WKE, manufactured by The Inktec): 100 parts, water: 20 parts, isopropyl alcohol: 20 parts
Water-based coating liquid a for adhesive layer ;
Carboxyl group- and hydroxyl group-containing aqueous urethane resin (Daiichi Kogyo Seiyaku Co., Ltd., F8583D): 100 parts, water-soluble epoxy crosslinking agent (Nagase Kasei Co., Ltd., Denacol 614B): 5 parts, water-dispersible isocyanurate bond-containing isocyanate Cross-linking agent (manufactured by Nikka Chemical Co., Ltd., X9003): 5 parts, water: 20 parts, isopropyl alcohol: 20 parts
Polyolefin resin for resin layer ;
Random polymerized polypropylene: 84 parts, low density polyethylene 15 parts, benzotriazole ultraviolet absorber: 0.5 parts, hindered amine light stabilizer: 0.3 parts, phenolic antioxidant: 0.2 parts
Water-based coating liquid C for protective layer ;
Water-based urethane resin-containing ink (manufactured by Showa Ink Industries, 135): 100 parts, water-dispersible isocyanurate bond-containing isocyanate cross-linking agent (manufactured by Nippon Polyurethane Industry Co., Ltd., AQ100): 10 parts, water: 20 parts, isopropyl Alcohol: 20 parts

(Example 2)
The following adhesive layer coating solution b was used in place of the adhesive layer aqueous coating solution a of Example 1. Otherwise, the decorative sheet of Example 2 was obtained in the same manner as Example 1.

Aqueous coating solution b for adhesive layer ;
Amino group-containing acrylic resin (Nippon Shokubai Co., Ltd., Polyment SK-1000): 40 parts, carboxyl group and hydroxyl group-containing aqueous urethane resin (Daiichi Kogyo Seiyaku Co., Ltd., F8583D): 60 parts, water-soluble epoxy resin (Nagase Kasei) Denacol 313): 10 parts, water: 10 parts, isopropyl alcohol: 10 parts

(Example 3)
The curing conditions of Example 1 were changed to curing for 3 days at a temperature of 40 ° C. using an oven. Otherwise, the decorative sheet of Example 3 was obtained in the same manner as Example 1.

(Comparative Example 1)
Instead of the adhesive layer aqueous coating solution a of Example 1, an adhesive layer aqueous coating solution c having the following composition was used. Otherwise, the decorative sheet of Comparative Example 1 was obtained in the same manner as Example 1.

Water-based coating solution c for adhesive layer ;
Carboxyl group- and hydroxyl group-containing aqueous polyurethane resin (Daiichi Kogyo Seiyaku Co., Ltd., F8583D): 100 parts, water-soluble epoxy crosslinking agent (manufactured by Nagase Kasei Co., Ltd., Denacol 614B): 10 parts, water: 20 parts, isopropyl alcohol: 20 copies

(Comparative Example 2)
A decorative sheet of Comparative Example 2 was obtained in the same manner as Comparative Example 1 except that the curing temperature was changed from 25 ° C to 80 ° C.

(Comparative Example 3)
Instead of the adhesive layer aqueous coating solution a of Example 1, an adhesive layer aqueous coating solution d having the following composition was used. Otherwise, the decorative sheet of Comparative Example 3 was obtained in the same manner as in Example 1.

A solvent-free coating solution d for the adhesive layer ;
Carboxyl group- and hydroxyl group-containing aqueous urethane resin (Daiichi Kogyo Seiyaku Co., Ltd., F8583D): 100 parts, water-dispersible isocyanurate bond-containing isocyanate crosslinking agent (manufactured by Nikka Chemical Co., Ltd., X9003): 10 parts, water: 20 Parts, isopropyl alcohol: 20 parts

(Evaluation method for each characteristic)
Evaluation of interlayer adhesion of each laminate obtained in Examples 1 and 2 and Comparative Examples 1 to 3, evaluation of interlayer adhesion after the weather resistance test, and evaluation of design were performed by the following methods. Moreover, the stability test of the aqueous coating liquid for adhesive layers used in Examples 1 and 2 and Comparative Examples 1 to 3 was performed by the following method. The obtained results are shown in Table 1.

(Interlayer adhesion evaluation method)
The laminate 1 cut to 1 inch in width was used as a test piece, and the base material 2 and the resin layer 4 of the test piece were used in an INSTRON 5500 tensile tester in a 25 ° C. atmosphere at a tensile rate of 100 mm / min. The tensile strength was evaluated under the condition of 180 ° between the resin layer 4 and the peel strength. Those having a peel strength of 10N or more were evaluated as “good”, and those less than 10N were expressed as “fail”.

(Evaluation method of boiling water resistance)
The boiling water resistance was evaluated by evaluating the interlaminar adhesion described above after the boiling water test, and the peel strength of 10N or more was evaluated as “good”, and less than 10N was rejected as “failed”. In the boiling water resistance test, the peel strength of the laminate 1 was measured by immersing the test piece of the laminate 1 in boiling water for 30 minutes and then drying it at room temperature for 24 hours.

(Design evaluation method)
For the design, before and after curing, the change in the wood grain pattern formed on the laminate 1 was visually determined, and a small change was indicated as “good” and a marked change was indicated as “fail”.

(Evaluation method for stability of aqueous coating solution for adhesive layer)
The water-based coating solution for the adhesive layer was used after 6 hours had passed after the preparation, and the layer adhesion and weather resistance test of the produced decorative sheet were judged as acceptable values, and the acceptable values were achieved. Those not present are represented by x.

It is sectional drawing which shows an example of the laminated constitution of the decorative sheet of this invention. It is sectional drawing which shows another example of the laminated constitution of the decorative sheet of this invention. It is sectional drawing which shows another example of the layer structure of the decorative sheet of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 101, 111 Laminated body 2 Base material 3 Adhesive layer 4, 4 ', 4 "Resin layer 5 Solid colored layer 6 Picture colored layer 7 Concavity and convexity 8 Partial colored layer 9 Protective layer 10 Primer layer 11 Colored layer 14 It consists of multilayers Resin layer 17 Concave part

Claims (6)

A resin having a hydroxyl group, a resin having a carboxyl group, an isocyanate group-containing compound, and an epoxy group-containing compound,
An aqueous coating solution for an adhesive layer, which causes a crosslinking reaction in a temperature range of at least 5 ° C to 40 ° C and a temperature range of 70 ° C to 180 ° C. A resin having a hydroxyl group and a carboxyl group, an isocyanate group-containing compound, and an epoxy group-containing compound,
An aqueous coating solution for an adhesive layer, which causes a crosslinking reaction in a temperature range of at least 5 ° C to 40 ° C and a temperature range of 70 ° C to 180 ° C. A resin having an amino group, a resin having a carboxyl group, and an epoxy group-containing compound,
An aqueous coating solution for an adhesive layer, which causes a crosslinking reaction in a temperature range of at least 5 ° C to 40 ° C and a temperature range of 70 ° C to 180 ° C. A laminate in which a base material, an adhesive layer, and a resin layer are laminated in this order,
A laminate comprising the adhesive layer formed of the aqueous coating liquid for an adhesive layer according to any one of claims 1 to 3. A method for producing a laminate in which a water-based coating liquid for an adhesive layer is applied on a substrate to form an adhesive layer, a resin layer resin is melt-extruded on the adhesive layer to form a resin layer, and then cured. Because
  The aqueous coating solution for an adhesive layer is the aqueous coating solution for an adhesive layer according to any one of claims 1 to 3,
  The adhesive layer is formed by causing a crosslinking reaction in a temperature region at the time of the melt extrusion, and by causing a crosslinking reaction in a temperature region at the time of the curing treatment,
  The temperature range at the time of the melt extrusion is a temperature range of 70 ° C to 180 ° C, and the temperature range at the time of the curing treatment is a temperature range of 5 ° C to 40 ° C. The said curing process is hold | maintained in the temperature range at the time of said curing using oven, The manufacturing method of the laminated body of Claim 5 characterized by the above-mentioned.

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