JP5096095B2 - Building material sheet using water-based adhesive and method for producing the same - Google Patents

Description

  The present invention relates to a building material sheet used for interiors of buildings, surface decorations of joinery, interiors of vehicles, and the like, and more particularly, and more specifically, at least two plastic sheets are laminated via an adhesive layer. The present invention relates to a sheet for building materials and a method for producing the same, and relates to a sheet for building materials laminated using a water-based urethane adhesive that does not contain a volatile tertiary amine, and a method for producing the same.

  As a building material sheet used for interiors of buildings, surface decoration of joinery, interiors of vehicles, etc., an ink layer consisting of a base material, a solid ink layer and / or a pattern ink layer, an adhesive layer and a transparent resin layer are sequentially laminated. Building material sheets are generally known. When manufacturing a sheet for building materials, a solvent-type adhesive has been proposed in consideration of various physical properties required for building materials as a composition of an adhesive used when laminating various sheets (Patent Document 1: Japanese Patent Laid-Open No. 2002-2002). No. 219785, Patent Document 2: JP 2004-339384 A).

  However, solvent-based adhesives may cause problems such as sick house syndrome if the organic solvent remains in the laminated sheets in addition to the effects on the human body due to organic solvents in the lamination work environment and air pollution problems. is there.

  Japanese Patent Laid-Open No. 8-120042 (Patent Document 3) proposes an aqueous resin of polyester urethane. The aqueous polyester urethane resin is produced by neutralizing an acid group-containing polyisocyanate with a base such as triethylamine, dispersing it in water, and extending the chain with a polyamine having an active hydrogen such as ethylenediamine. is there. Although this method is an excellent method for obtaining an aqueous dispersion of a high molecular weight polyester urethane resin without using an organic solvent or with a small amount of organic solvent, the component usable as a base is reactive with isocyanate. There is no tertiary monoamine. However, since tertiary amines are volatile, they have problems such as human influence and air pollution. On the other hand, when a primary or secondary amine having active hydrogen is used as a neutralizing agent, the reaction with isocyanate proceeds and sufficient target emulsifying ability cannot be obtained, resulting in an unstable dispersion or gelled resin. There is a problem that gives.

  Thus, although the water-based polyester urethane resin of Reference 3 has the effect of reducing the organic solvent, since it contains a tertiary amine compound, the volatile amine spreads in the working atmosphere during the lamination, thereby improving the health of the worker. Even when the amine remains in the film after lamination, there still remains a problem of fear of odor and toxicity.

In addition, in the neutralization of a relatively high molecular weight polyester polyurethane polyol resin having an acid value in a solvent in advance, there is no particular limitation on synthesis if the base type is monovalent, but a relatively large amount of organic solvent is used. Therefore, it is difficult to obtain a higher molecular weight polyester polyurethane resin, and it is an excellent method for the purpose of reducing organic solvents. Absent.
As described above, the conventional method for producing an aqueous dispersion of a polyester polyurethane resin has a limit in reducing both the organic solvent and the volatile amine.

  Japanese Patent No. 2909939 (Patent Document 4) proposes a two-part aqueous resin obtained by adding a polyisocyanate to a polyurethane resin that can be diluted with water. Since the isocyanate group is deactivated by water, the behavior of the cured film properties obtained is different immediately after blending with the curing agent and several hours after blending, for example, adhesive strength and weather resistance are likely to vary. There's a problem.

JP 2002-219785 A JP 2004-339384 A JP-A-8-120042 Japanese Patent No. 2909939

  The present invention has been accomplished in view of the above circumstances, and the problem to be solved by the present invention is for building materials that avoid the above-mentioned air pollution problems and effects on the human body and exhibit stable physical properties. A sheet and a manufacturing method thereof are provided.

  As a result of intensive studies in view of the above problems, the present inventors have found that an aqueous polyester polyurethane resin obtained by reaction with polyester polyisocyanate and polyamine in the presence of a neutralized product of carboxyl group-containing polyurethane polyol, and a curing agent The two-component curable resin composition obtained by blending with the polyisocyanate as described above has stable adhesive performance, and a building material sheet using the resin composition as an adhesive and a method for producing the same are completed. It was.

  Furthermore, the present inventors have high reactivity with an alkali metal ion or a polyisocyanate as a curing agent as a base for promoting emulsification of a carboxyl group-containing polyurethane polyol in an adhesive using the two-component curable resin composition. It has been found that an aqueous polyester polyurethane resin can be obtained very stably by employing an amine containing active hydrogen, and the present inventors have further demonstrated that the terminal hydroxyl group of the aqueous polyester urethane is highly reactive with isocyanate. It has been found that by using a specific hydroxyl group, more stable adhesive performance is exhibited, and the present invention has been completed.

That is, the present invention provides the following 1. -10. It is the manufacturing method of the sheet | seat for building materials shown in this, and this sheet | seat.
1. A building material sheet comprising at least a base material and a transparent resin layer laminated via an adhesive layer, the adhesive layer comprising:
Aqueous polyester polyurethane resin (1) obtained by reaction with polyester polyisocyanate (b) and polyamine (c) in the presence of a neutralized product of carboxyl group-containing polyurethane polyol (a), and polyisocyanate ( 2) and
It is formed using the curable resin composition (3) containing this, The sheet | seat for building materials characterized by the above-mentioned.
2. 1. The carboxyl group of the carboxyl group-containing polyurethane polyol (a) is neutralized with any of alkali metal ions selected from lithium ions, sodium ions, and potassium ions. The building material sheet according to 1.
3. 1. The carboxyl group of the carboxyl group-containing polyurethane polyol (a) is neutralized with a primary or secondary amine. The building material sheet according to 1.
4). The carboxyl group-containing polyurethane polyol (a) has an acid value of 30 to 60 mgKOH / g and a hydroxyl value of 10 to 60 mgKOH / g. To 3. The sheet | seat for building materials of any one of these.
5. The end of the carboxyl group-containing polyurethane polyol (a) is a hydroxyl group modified with any one selected from 1,4-butanediol, diethylene glycol, and 1,6-hexanediol. To 4. The sheet | seat for building materials of any one of these.
6). The polyester polyisocyanate (b) has an acid value of 0 to 12 mgKOH / g. To 5. The sheet | seat for building materials of any one of these.
7). 1. The blend ratio of the carboxyl group-containing polyurethane polyol (a) and the polyester polyisocyanate (b) is (a) :( b) = 10: 90 to 50:50 mass%. To 6. The sheet | seat for building materials of any one of these.
8). The building material sheet is a building material sheet having at least a base material, an ink layer, an adhesive layer, and a transparent resin layer, wherein the respective layers are sequentially laminated. To 7. The sheet | seat for building materials of any one of these.
9. In the presence of a neutralized product obtained by neutralizing the carboxyl group of the carboxyl group-containing polyurethane polyol (a) with any of alkali metal ions selected from lithium ions, sodium ions, and potassium ions, or primary or Aqueous polyester polyurethane resin (1) comprising a high molecular weight product of polyester polyurethane polyurea by reaction with polyester polyisocyanate (b) and polyamine (c) in the presence of a neutralized product neutralized with a secondary amine. (A) to obtain
A step (B) of obtaining a curable resin composition (3) by blending the polyisocyanate (2) with the aqueous polyester polyurethane resin (1) obtained by the step (A);
Using the curable resin composition (3) obtained in the step (B), laminating at least the base material and the transparent resin layer (C),
A method for producing a sheet for building materials.
10. An aqueous polyester polyurethane resin (1) comprising a high molecular weight product of polyester polyurethane polyurea by reaction with polyester polyisocyanate (b) and polyamine (c) in the presence of a neutralized product of the carboxyl group-containing polyurethane polyol (a). How to get
The neutralized product of the carboxyl group-containing polyurethane polyol (a) and the polyester polyisocyanate (b) are mixed, and water is further mixed to obtain an emulsion.
8. The above-mentioned 9. characterized in that polyamine is mixed with the obtained emulsion to extend the chain. The manufacturing method of the sheet | seat for building materials as described in 2.
In the present specification, “aqueous” refers to a property of a resin that can be dissolved or dispersed in water (or a mixed solvent of a water-miscible solvent such as alcohol and water) and used for the resin (eg, “ “Aqueous resin”) and “aqueous” are used for agents obtained by dissolving or dispersing the aqueous resin in the above-mentioned solvent (eg, “aqueous coating agent”, “aqueous adhesive”).

  The building material sheet of the present invention is a two-component composition comprising, in the above-described layer configuration, a curable resin composition (3) used for an adhesive layer and an aqueous polyester polyurethane resin (1) having a specific composition and a polyisocyanate (2). Since the curable resin composition is used as a water-based adhesive, both organic solvents and volatile amines can be reduced, so air pollution problems and effects on the human body can be avoided, and adhesion strength is improved and excellent. Stable physical properties such as weather resistance.

Hereinafter, the present invention will be described in more detail.
FIG. 1 is a cross-sectional view showing an example of the simplest layer structure of the building material sheet of the present invention. In FIG. 1, 1 shows an example of the building material sheet of the present invention, and the building material sheet 1 includes a base material 2, an ink layer 3, an adhesive layer 4, and a transparent resin layer 5 laminated in this order. Has been. As for the ink layer 3, it is common that the pattern ink layer is laminated | stacked on the solid ink layer. A back surface primer layer 6 may be further provided on the back surface of the base material 1 in the building material sheet of FIG. 1 in order to facilitate attachment to the surface of the building material such as a wood base material, and the transparent resin layer 5 A surface protective layer 7 may be further provided on the surface.

  FIG. 2 is a cross-sectional view showing an example of a general layer structure of the building material sheet of the present invention. In FIG. 2, 11 shows another example of the sheet | seat for building materials of this invention. The building material sheet 11 is provided with an uneven pattern 8 by embossing or the like on the surface of the transparent resin layer 5 of the building material sheet 1 shown in FIG.

  FIG. 3 is a cross-sectional view showing another example of a general layer structure of the building material sheet of the present invention. In FIG. 3, a building material sheet 21 is provided with a surface primer layer 9 between the transparent resin layer 5 and the surface protective layer 7 of the building material sheet 11 shown in FIG. .

FIG. 4 is a cross-sectional view showing an example in which the building material sheet of the present invention is laminated on an adherend (backing material) that is a three-dimensional article.
FIG. 5 is a cross-sectional view showing an example in which the building material sheet of the present invention is laminated on a flat plate or curved plate or sheet (or film).

Adhesive layer The curable resin composition used to form the adhesive layer is shown below.
The curable resin composition (3) used in the present invention is a two-component curable type (that is, a two-component hard resin composition) used as an aqueous adhesive, and is a neutralized product of a carboxyl group-containing polyurethane polyol (a). In the presence of water-based polyester polyurethane resin (1) obtained by reaction with polyester polyisocyanate (b) and polyamine (c), and polyisocyanate (2) as a curing agent.

(1) About water-based polyester polyurethane resin In manufacturing a carboxyl group-containing polyurethane polyol (a), a polyester polyol is first synthesized. The raw material that can be used for the synthesis of the polyester polyol is not particularly limited, and the polyester polyol can be synthesized by dehydration condensation of a known polyol and a polycarboxylic acid or a ring-opening reaction of a cyclic ester such as caprolactone. Specifically, examples of the polyol component include ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, cyclohexanedimethanol, trimethylolethane, trimethylolpropane, and the like. Examples of the polycarboxylic acid include maleic acid, succinic acid, adipic acid, cyclohexanedicarboxylic acid, sebacic acid, azelaic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and anhydrides thereof.

  The method for synthesizing the polyester polyol is not particularly limited. The above polyol and polycarboxylic acid are mixed, dehydrated and condensed in the range of about 150 ° C. to 250 ° C., and synthesized by performing an esterification reaction under reduced pressure as necessary. be able to.

  The polyester polyol for producing the carboxyl group-containing polyurethane polyol (a) is preferably one having at least two hydroxyl groups in one molecule, and when the number of hydroxyl groups is less than 2, Sufficient high molecular weight does not advance, and adhesive strength and weather resistance may not be sufficiently obtained. Further, when the average number of hydroxyl groups contained in one molecule is 2.5 or more, the viscosity becomes high during the urethanization step, and the desired emulsifying ability may not be obtained sufficiently. The average number of hydroxyl groups contained in one molecule of polyol is preferably in the range of about 2.0 to 2.2. The hydroxyl value is preferably 40 to 70 mgKOH / g, and the acid value is preferably 0 to 30 mgKOH / g.

  The polyester polyol thus obtained is derived into a carboxyl group-containing polyurethane polyol (a). That is, dimethylolpropionic acid or dimethylolalkanoic acid such as dimethylolbutanoic acid is added so that the acid value is 30 to 60 mgKOH / g and the hydroxyl value is 10 to 60 mgKOH / g, and reacted with polyisocyanate. It reacts with glycol via the polyester polycarboxylic acid of isocyanate, and the terminal is converted into a hydroxyl group to obtain the target carboxyl group-containing polyurethane polyol (a). When the acid value of the carboxyl group-containing polyurethane polyol (a) is less than 30 mgKOH / g, the emulsifying ability of the polyester polyisocyanate (b) described later is deteriorated, and when the acid value is more than 60 mgKOH / g, the water resistance is deteriorated. Moreover, when the hydroxyl value is less than 10 mgKOH / g, the viscosity of the carboxyl group-containing polyurethane polyol (a) is high and handling becomes difficult, and when the hydroxyl value exceeds 60 mgKOH / g, the water resistance is deteriorated. The polyisocyanate that can be used here is preferably an aliphatic isocyanate compound in consideration of weather resistance, and specifically, hexamethylene diisocyanate, isophorone diisocyanate, or the like. As the glycol for conversion, conversion by glycol having a hydroxyl group having high reactivity with an isocyanate group contained in a curing agent combined as a two-part curable resin composition is desirable. Specifically, 1,4-butane is used. Diol, diethylene glycol, 1,6-hexanediol and the like are desirable. When the hydroxyl group is introduced by the glycol, it is difficult to be affected by moisture remaining in the film after lamination, and is hardly affected by temperature and humidity during aging, so that stable adhesive performance is exhibited.

  The resulting carboxyl group-containing polyurethane polyol (a) is then neutralized with an alkali metal salt that can be used as a base, or an alkali metal ion, or a primary or reactive hydrogen having an active hydrogen reactive with an isocyanate group. Neutralize with secondary amine. The amount of base to be neutralized is preferably the same amount of base as the number of carboxyl groups.

  Examples of the alkali metal salt that can be used as the base include lithium hydroxide, sodium hydroxide, and potassium hydroxide. In view of the viscosity and water dispersibility of the resulting aqueous dispersion, potassium hydroxide is particularly desirable. An aqueous solution of potassium hydroxide of about 40% to 40% is prepared, and the aqueous solution may be added while stirring the carboxyl group-containing polyurethane polyol (a).

  In addition, a monovalent primary or secondary amine that can be used as a base and has an active hydrogen reactive with an isocyanate group is preferably a monovalent primary or secondary amine, specifically, ammonia, methyl Examples include amine, ethylamine, butylamine, ethanolamine, propanolamine, dibutylamine, morpholine, diethanolamine and the like. In view of odor reduction and storage stability, it is desirable to use ethanolamine or diethanolamine. Neutralization with these isocyanate groups and reactive amines is carried out by blending the polyisocyanate (2) as a curing agent, and then the primary or secondary amine that has acted as a neutralizing agent in the curing process. Since it reacts with the isocyanate group in the isocyanate (2) and is incorporated into the film as a urea bond as a polymer, it is advantageous not only to promote improvement in water resistance and weather resistance, but also to suppress volatilization of amine compounds. effective. Furthermore, a tertiary amine can be used as a base. A tertiary amine that can be used is a monovalent amine having at least one hydroxyl group in one molecule. Specifically, dimethylethanolamine, diethylethanolamine, methyldiethanolamine, triethanolamine, etc. Can be mentioned. Use of these tertiary amines having a hydroxyl group is advantageous in that volatilization of amines can be suppressed since polyisocyanates as curing agents are blended and then incorporated into the film as urethane bonds in the curing process. There is a great effect.

  Next, the manufacturing method of polyester polyisocyanate (b) is demonstrated. The polyester polyisocyanate (b) can be produced from a polyester polyol for producing a carboxyl group-containing polyurethane polyol (a). If necessary, dimethylolalkanoic acid is added, and isophorone diisocyanate, tetramethylxylylene diisocyanate, etc. A resin having a terminal isocyanate group may be modified with urethane using an aliphatic polyisocyanate.

  The polyester polyisocyanate (b) preferably has a molecular weight of about 2000 to 4000. If the molecular weight is 2000 or less, sufficient adhesive strength may not be obtained. If the molecular weight is 4000 or more, the polyester polyisocyanate (b) The viscosity of the water tends to increase and the water dispersibility tends to deteriorate. Further, the acid value of the polyester polyisocyanate (b) is preferably in the range of 0 to 12 mgKOH / g, and when the acid value exceeds 12 mgKOH / g, the water resistance may be insufficient. The acid value is preferably about 0 to 10 mgKOH / g.

  Next, the water dispersion of the polyester polyisocyanate (b) by the neutralized product of the carboxyl group-containing polyurethane polyol (a) obtained above will be described in detail. The polyester polyisocyanate (b) itself does not have water dispersibility, but in the presence of a neutralized product of the carboxyl group-containing polyurethane polyol (a), it is poured into water to give a stable emulsion. The mixing ratio of the neutralized product of the carboxyl group-containing polyurethane polyol (a) and the polyester polyisocyanate (b) is (a) :( b) = 10: 90 to 50: 50% by mass. When (a) is less than 10% by mass, sufficient emulsifying ability may not be obtained, and when (a) exceeds 50% by mass, water resistance may be deteriorated. Also, the acid value of the resin mixture after blending is preferably in the range of 8 to 20 mg KOH / g, and when the acid value of the resin mixture after blending is less than 8 mg KOH / g, a sufficient emulsion stabilization effect cannot be obtained. In addition, when the acid value of the resin mixture after blending exceeds 20 mgKOH / g, the water resistance may deteriorate. Further, desirably, the acid value of the resin mixture after blending is preferably in the range of 10 to 16 mg KOH / g.

  When the polyester polyisocyanate (b) has an acid value, an alkali metal ion in an amount that neutralizes the acid value of the polyester polyisocyanate (b) in the neutralized product of the carboxyl group-containing polyurethane polyol (a) or 1 A secondary or secondary amine can be added in advance as a neutralizing agent. However, when the neutralizing agent is a primary or secondary amine, in particular, the carboxyl group-containing polyurethane is mixed with the neutralized product of the carboxyl group-containing polyurethane polyol (a) and the polyester polyisocyanate (b). Since the primary or secondary amine existing in excess in the polyol (a) may react with the isocyanate group of the polyester polyisocyanate (b), the acid of the polyester polyisocyanate (b) used in the water dispersion step It is advisable to add in the water an amount of primary or secondary amine sufficient to neutralize the value by 100%.

Subsequently, the neutralized product of the carboxyl group-containing polyurethane polyol (a) and the polyester polyisocyanate (b) are mixed, and water is further mixed to obtain an emulsion (aqueous dispersion).
The resulting emulsion (aqueous dispersion) is subsequently chain extended with polyamine. Let the emulsion obtained from this be water-based polyester polyurethane resin (1). Examples of polyamines that can be used include ethylenediamine, 1,3-propylenediamine, 2- (2-aminoethylamino) ethanol, 1,6-hexamethylenediamine, isophoronediamine, diethylenetriamine, and the like, one or two of these. The above can also be mixed and used. Further, as the terminator, a hydroxyl group-containing monoamine compound such as ethanolamine, propanolamine, diethanolamine and the like is good, and a resin derived from polyester polyisocyanate (b), an extender polyamine and a terminator hydroxyl group-containing monoamine. As the hydroxyl value, it is preferable to introduce a hydroxyl group in the range of 5 to 20 mgKOH / g. When it is less than 5 mgKOH / g, the reaction rate with the curing agent is lowered, and the adhesion performance may not be stable. Further, when it exceeds 20 mgKOH / g, the water resistance may be deteriorated. Therefore, the hydroxyl value of the resin derived from the polyester polyisocyanate (b), the polyamine as an extender, and the monoamine containing a hydroxyl group as a terminator, More preferably, it is 8-15 mgKOH / g.

  The solid content of the water-based polyester polyurethane resin (1) is preferably in the range of approximately 30% to 50%, and if it is less than 30%, it is necessary to volatilize a large amount of water when applying the adhesive. Problems with workability occur. Further, when the content is 50% or more, the viscosity of the aqueous dispersion becomes high. More desirably, the solid content of the aqueous dispersion is in the range of 35% to 45%.

(2) Polyisocyanate used as a curing agent As the polyisocyanate (2) used as a curing agent, a polyisocyanate based on hexamethylene diisocyanate was modified with a polyethylene glycol chain that was dispersed only in water. Nonionic polyisocyanates are preferred. Examples of polyisocyanates based on hexamethylene diisocyanate include burette types, nurate types, and allophanate types, and these can be used alone or in combination of two or more.
The polyethylene glycol chain to be modified is preferably a monoalcohol obtained by addition reaction of ethylene oxide with a monohydric alcohol such as methanol, ethanol, propanol or butanol as an initiator.

  As the amount of the polyethylene glycol chain to be modified increases, the dispersibility in water increases, but on the other hand, the pot life after blending is shortened, the water resistance is poor, and the crosslinking density is reduced. It is desirable to adjust the amount so that the NCO% of the finally obtained curing agent does not fall below 14%, because it causes defects.

  Further, in order to develop a stable adhesive strength, the isocyanate average functional group number of the obtained curing agent is desirably 2.5 or more, and if it is less than 2.5, sufficient crosslinking density cannot be obtained, and weather resistance and resistance May cause problems such as hot water.

  The aqueous polyester polyurethane resin (1) thus obtained is used as a curable resin composition (3) formed by blending with the polyisocyanate (2) as the curing agent. The mixing ratio of the water-based polyester polyurethane resin (1) and the polyisocyanate (2) is a mass ratio, the solid content of the water-based polyester polyurethane resin (1): the solid content of the polyisocyanate (2) = 90: 10 to 70:30. The ratio of the number of isocyanate groups in the polyisocyanate (2) as the curing agent to the number of hydroxyl groups in the solid content of the aqueous polyester polyurethane resin (1) is about 1: 5 to 1: 7. It is desirable to blend in. Moreover, it can dilute with water so that it may become a suitable viscosity.

  The method for laminating at least the base material and the transparent resin layer via the adhesive layer is not particularly limited. For example, a film-like transparent resin layer may be bonded with a commonly used dry laminator or thermal laminator or the like, or the transparent resin layer is melt-extruded and applied onto the substrate via the adhesive layer. Or can be laminated by other known methods.

The base material is an essential component in the building material sheet, and an olefin resin can be preferably applied, but the type is not limited. For example, (a) the main raw material is composed of either high-density polyethylene or polypropylene as a hard segment, and a mixture obtained by adding an elastomer and an inorganic filler as a soft segment can be used as a base material. In addition, (b) ethylene-propylene-butene copolymers described in JP-A-9-1111055, JP-A-5-77371, JP-A-7-316358 and the like can be used as a substrate. Also, (c) a mixture of isotactic polypropylene as a hard segment and atactic polypropylene as a soft segment described in JP-B-6-23278 can be used as a substrate.

  The high-density polyethylene as the hard segment in the olefin resin (a) is preferably polyethylene having a specific gravity of 0.94 to 0.96, and has a high degree of crystallinity obtained by the low-pressure method. High-density polyethylene, which is a polymer with few branched structures, 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 formed by adding a hydrogen atom to at least a part of the double bond of the diene rubber molecule, and suppresses 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 that can be copolymerized with two or more olefins is added. As the olefin, ethylene, propylene, α-olefin, or the like is used. 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 added amount of these elastomers is 10 to 60% by mass, preferably about 30% by mass. If the content is lower than 10% by mass, the change in the constant load elongation becomes too steep, and the elongation at break, impact resistance, and easy adhesion decrease. If the content is higher than 60% by mass, the transparency, weather resistance and resistance Decrease in creep properties occurs.

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

  As the (b) 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 of a terpolymer of ethylene, propylene and butene described in JP-A-9-1111055. The mass ratio of the monomer component is preferably 90% by mass or more for propylene, and the melt flow rate is preferably 1 to 50 g / 10 min under the conditions of 230 ° C. and 2.16 kg. With respect to 100 parts by mass of such a ternary random copolymer, the random copolymer comprises 0.01 to 50 parts by mass of a transparent nucleating agent mainly composed of a phosphoric acid aryl ester compound, and 12 to 12 carbon atoms. It is obtained by melt-kneading 0.003 to 0.3 parts by mass of 22 fatty acid amides. (B) A terpolymer of ethylene, propylene and butene described in JP-A-5-77371, wherein the propylene mass ratio is 20 to 100 mass% of an amorphous polymer, An ethylene-propylene-butene copolymer obtained by adding 80 to 0% by mass of crystalline polypropylene. (C) A terpolymer of ethylene, propylene and 1-butene described in JP-A-7-316358, wherein the content of propylene and / or 1-butene is 50% by mass or more. An oil gelling agent such as an N-acylamino acid amine salt or N-acylamino acid ester is added to a composition in which 80 to 0% by mass of a crystalline polyolefin such as isotactic polypropylene is mixed with 20 to 100% by mass of the coalescence. An ethylene-propylene-butene copolymer added by 0.5% by mass.

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

  As the olefin-based resin (C), the number average molecular weight Mn is 25000 or more as a soft segment described in Japanese Patent Publication No. 6-23278, and the ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn. 10 to 90% by mass of atactic polypropylene soluble in boiling heptane of ≦ 7 and (B) 90 to 10 mass of isotactic polypropylene insoluble in boiling heptane having a melt index of 0.1 to 4 g / 10 min as a hard segment % And a soft polypropylene which consists of a mixture with%.

  Among the olefin-based thermoplastic elastomers of (c) above, those composed of a mixture of isotactic polypropylene and atactic polypropylene and having a mass ratio of atactic polypropylene of 5 to 50% by mass are preferred, and the mass ratio of atactic polypropylene Is particularly preferable. When the mass ratio of the atactic polypropylene is less than 5% by mass, it is embossed, or unevenly deformed by necking when it is molded into a three-dimensional or concavo-convex article, resulting in wrinkles and patterns Distortion occurs. On the other hand, if the mass ratio of the atactic polypropylene exceeds 50% by mass, the sheet itself is easily deformed. When the sheet is passed through a printing machine, the sheet is deformed, and the pattern of the ink layer is distorted. Defects such as mismatching are likely to occur, 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 base as necessary.

  Coloring agents include titanium white, zinc white, bengara, vermilion, ultramarine blue, 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. In addition, if necessary, inorganic fillers may be added, and powders such as calcium carbonate, barium sulfate, clay, talc, silica (silicon dioxide), alumina (aluminum oxide), etc. may be mentioned. Usually, it is 5 to 60% by mass. The colorant is added to give the base material the color necessary as a building material sheet, and may be either transparent coloring or opaque (concealment) coloring. However, in general, the coating material to which the building material sheet is attached is used. Opaque coloring is preferred to conceal the kimono.

  Known heat stabilizers such as phenolic, sulfite-based, phenylalkane-based, physphite-based, and amine-based ones can be used, and are used to improve the prevention of deterioration such as thermal discoloration during heat processing. . 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, oxidation Inorganic substances such as cerium 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 0.5-10 mass% 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 can be obtained by forming a film by arbitrarily selecting and blending the above-described materials by a conventional method such as calendering. The thickness of the base material is 50 to 200 μm, preferably about 100 μm.

  The surface of the base material on the surface side (transparent resin layer side) of the building material sheet is subjected to easy adhesion treatment such as application of a primer layer (also referred to as an easy adhesion layer or an anchor layer), corona discharge treatment, plasma treatment, ozone treatment, etc. It is preferable to apply. As the primer layer, acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester resin, polyurethane resin, chlorinated polypropylene, and chlorinated polyethylene can be used.

  In addition to the base material 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, an ethylene-vinyl acetate copolymer, Vinyl resins such as ethylene-vinyl alcohol copolymers, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, acrylic resins such as polymethyl methacrylate, polymethyl acrylate, and polyethyl methacrylate, polystyrene, acrylonitrile-butadiene-styrene It is also possible to use a sheet or film made of a resin such as a copolymer (ABS), cellulose triacetate, cellophane, or polycarbonate. 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 raw material obtained by sol coating or dry laminating vinyl can be used. It is also possible to use a sheet or film made of inorganic fibers such as glass fibers, asbestos, potassium titanate fibers, alumina fibers, silica fibers, and carbon fibers. Moreover, metal foils, such as aluminum, iron, stainless steel, copper, etc. can also be used. Furthermore, it is also possible to use a material obtained by laminating a plurality of such base materials as a base material.

The ink layer is an important layer in the building material sheet and is composed of a solid ink layer and / or a pattern ink layer. The solid ink layer is provided for the purpose of concealing the background of the base material, and is usually formed as an all-solid colored layer having no pattern. The pattern ink layer generally has a pattern or color consisting of a wood grain pattern, stone pattern, cloth pattern, leather pattern, geometric pattern, etc., depending on figures, characters, symbols, colors, combinations thereof, etc. On top, it is formed as a planar, concavo-convex, or convex layer. In some cases, the pattern ink layer also functions as a solid ink layer. In this case, the pattern ink layer becomes a solid ink layer. The solid ink layer and / or the pattern ink layer thus formed may be provided on the entire surface of the substrate surface or may be provided partially. The ink layer can also be composed of a solid ink layer provided on the entire surface of the substrate and a pattern ink layer partially provided on the surface of the solid ink layer. As the forming material, an appropriate material that has been conventionally used for forming an ink layer of a building material sheet can be used without particular limitation. The ink layer forming material includes polyurethane, polyester, polyacrylate, polyurethane acrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate copolymer, rosin derivative, styrene-anhydrous malein. Examples of the water-based or solvent-based coating agent include an alcohol adduct of an acid copolymer, a cellulose resin, and a mixture of these resins.

  In the present invention, one or both of the solid ink layer and the pattern ink layer are preferably formed of an aqueous coating agent, and more preferably an aqueous polyurethane resin is an essential resin component (hereinafter also referred to as a resin component). It is desirable to be formed with an aqueous coating agent contained as For example, it is preferable to use an aqueous coating agent containing an aqueous polyurethane resin as a resin component, and apply and dry the aqueous coating agent to form one or both of a solid ink layer and a pattern ink layer. Since these water-based coating agents reduce the use of VOCs, the generation of VOCs in the work environment or living space can be suppressed, and the safety of the working environment and living space can be further improved. Can do. Furthermore, since the resin component constituting the ink layer formed with the water-based coating agent is an aqueous polyurethane resin, in addition to the interlayer adhesion of the adhesive layer, the ink layer of the present invention comprises a substrate and a transparent resin layer. Interlayer adhesion can be improved.

  The reason why interlaminar adhesion is improved by forming a solid ink layer and / or a pattern ink layer with a polyurethane resin is presumed to have both flexibility and followability and high internal cohesion in the layer. The

  Coloring agents such as coloring pigments and dyes are blended in the aqueous coating agent used for the solid ink layer and the pattern ink layer. In addition, additives such as waxes, dispersants, antifoaming agents, leveling agents, stabilizers, fillers, lubricants, lubricants, antioxidants, UV absorbers, light stabilizers, etc. are optionally added, water Alternatively, a water-based coating agent is prepared by using a water-based mixed solvent composed of water and alcohol and thoroughly mixing with a mixer or the like.

  As the color pigment, a commonly used organic or inorganic pigment can be used. Among these colored pigments, yellow pigments include azo pigments such as monoazo, disazo, and polyazo, organic pigments such as isoindolinone, yellow lead, yellow iron oxide, cadmium yellow, titanium yellow, antimony yellow, quinophthalone, and quinocone. Inorganic pigments such as salindione can be used. 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. Further, fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants, and the like can be optionally contained.

  The solid ink layer and the pattern ink layer are formed by providing the above-described aqueous coating agent by coating or printing and then drying. More specifically, the solid ink layer is usually formed by applying or printing a water-based coating agent for a solid ink layer, followed by drying and curing. The pattern ink layer is formed by using a water-based coating agent for the pattern ink layer. After printing, it is formed 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. A method such as flow coating or brush coating can be used, and the coating is performed so that the film thickness after drying is about 1.0 to 10 μm. 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.

  By forming an ink layer composed of a solid ink layer and / or a pattern ink layer with such a water-based coating agent, the initial objective of the present invention is to improve the environmental safety and the interlayer adhesion of the building material sheet. be able to.

Transparent resin layer The transparent resin layer, also called the top resin layer, protects the ink layer from scratches, etc., improves the surface strength of the building material sheet, and gives a feeling of painting. On the ink layer.

  The resin constituting the transparent resin layer is not particularly limited as long as it is a transparent resin that is well formed on the ink layer through the above-described adhesive layer. For example, an olefin-based material such as transparent polypropylene is used. A resin can be preferably mentioned. As the resin other than the olefin resin that can be used as the resin for the transparent resin layer, the same material as the constituent material of the above-mentioned base material can be used, and the resin for forming such a transparent resin layer, if necessary, It can be formed by adding known additives such as colorants, fillers, UV absorbers, light stabilizers, matting agents, etc., and can be formed into a colored transparent resin layer or transparent or translucent with UV absorption characteristics It can be a resin layer.

  As a method for forming the transparent resin layer, a transparent resin sheet formed separately can be laminated on the adhesive layer, or can be formed by a melt extrusion coating method, or can be laminated by other known methods.

  Further, the transparent resin layer may have a multilayer structure of two or more layers. The transparent resin layer formed by laminating two or more layers is advantageous in that different effects can be imparted to the transparent resin layer on the substrate side and the transparent resin layer on the surface protective layer side. For example, specifically, by forming the transparent resin layer on the surface protective layer side with a resin whose main component is a fluorine-based resin such as vinylidene fluoride, it is possible to impart excellent surface functions such as stain resistance. The transparent resin layer on the base material side is formed of a thermoplastic acrylic resin or the like, and can be laminated so that adhesion between the adhesive layer and the like can be improved. In addition, by forming the transparent resin layer on the surface protective layer side with a polypropylene resin to which a weathering agent is added, excellent weather resistance can be imparted, and the transparent resin layer on the base material side is a polypropylene type containing an elastomer. By forming the resin, it can be laminated so that the weather resistance and adhesion can be improved.

  The two or more transparent resin layers can be formed by melt-coextrusion of a plurality of resin compositions, or can be formed by various lamination methods such as dry lamination and thermal lamination. At this time, a transparent resin layer composed of two or more layers can be formed via an easy-adhesion layer acting as a primer layer or an anchor layer. In this case, the easy-adhesion layer can be formed by melt coextrusion together with the transparent resin layer.

The transparent resin layer is preferably applied at a coating amount of about 15 to 400 g / m ² so that the thickness of the transparent resin layer is about 20 to 300 μm.

  An uneven pattern 8 as shown in FIG. 3 may be formed on the surface of the transparent resin layer as necessary. The uneven pattern is also called an embossed pattern. In addition, when two or more transparent resin layers are formed, the concavo-convex pattern can be formed on the transparent resin layer on the outermost surface, or can be formed on the transparent resin layer other than the outermost surface, which is arbitrarily performed be able to.

  The uneven pattern is not particularly limited as long as it is a pattern according to the use of the building material sheet. For example, wood grain conduit groove, wood grain annual ring irregularity, floatation annual ring irregularity, wood grain irregularity, sand grain, satin, hairline, line-like groove, granite cleaved surface texture, textured surface texture, skin squeezing, text, geometry You can list patterns such as academic patterns.

  Examples of means for forming the concavo-convex pattern include an embossing method by heat and pressure and a T-die melt extrusion method. The embossing method by heat and pressure is a method of softening the surface of the transparent resin layer by heating, pressurizing the surface with an embossing plate to form an uneven pattern on the embossing plate, cooling and fixing the surface. A single-wafer or rotary embossing machine can be used. When forming by the embossing method, the embossing is performed in advance on the resin sheet to be the transparent resin layer before lamination by laminating, or the resin sheet to be the transparent resin layer is laminated at the same time (so-called doubling embossing method) can do. In addition, when laminating a transparent resin layer by the T-die melt extrusion method, it is possible to form a concavo-convex pattern simultaneously with the formation and lamination of the transparent resin layer by using a cooling roller that also serves as a shaping roller. . The embossed pattern can also be formed by hairline processing, sandblasting, or the like.

Surface protective layer The surface protective layer is also referred to as a topcoat layer or an overprint layer (OP layer), and is provided for the purpose of protecting the building material sheet by covering the surface of the concavo-convex pattern.

  Since the surface protective layer is used for the purpose of improving physical properties such as scratch resistance and contamination 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 agent, in consideration of environmental safety that suppresses the occurrence of VOC, the same aqueous coating agent used for forming the ink layer and the adhesive layer described above, and It is desirable to form with a solvent-type coating agent. When a solvent-free coating agent is used, an ionizing radiation curable coating agent is preferable. Therefore, in the same manner as the aqueous adhesive described above, an aqueous resin such as an aqueous polyurethane resin is used, and further, a colorant, a dispersant, an antifoaming agent, a leveling agent, a stabilizer, a filler, a lubricant, a lubricant, and an antioxidant. , UV absorbers, light stabilizers, and other additives, water-based coating agents prepared by mixing thoroughly with a mixer or the like using a water solvent or a mixed solvent consisting of water and alcohol, etc. Can be used.

  Moreover, a surface protective layer can also be formed with the reaction type aqueous resin composition, and scratch resistance and adhesiveness with a transparent resin layer can be improved. In particular, when an emulsion type resin is used, a reaction initiator such as a curing agent is incorporated into the resin composition and protected, and the reaction can be started after coating. Therefore, it is possible to form a surface protective layer by coating with a resin composition that is easy to apply and then reacting. Examples of such a reactive resin composition include, as a heat-sensitive reaction resin, a main agent composed of a resin such as polyurethane, polyacrylate or polyurethane acrylate having an active hydrogen group, an isocyanate group, solvent water or an alcohol compound. A main component comprising a resin composition having an amino group or a carboxylic acid group, or a resin composition obtained by emulsifying an isocyanate curing agent that has been hydrophilically treated or an isocyanate curing agent that has been treated with a blocking agent. And a resin composition comprising a water-soluble or water-dispersible curing agent having an epoxy group, a carbodiimide group, or an oxazoline group.

  The ionizing radiation curable resin is a resin that undergoes a cross-linking polymerization reaction by irradiation with ionizing radiation and changes to a three-dimensional polymer structure. The ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing and crosslinking molecules, visible light, ultraviolet light (including near ultraviolet light, vacuum ultraviolet light, etc.), X-ray, electron beam, ion. There are lines. Usually, ultraviolet rays or electron beams are used. As the ultraviolet light source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp can be used. As the wavelength of ultraviolet rays, the wavelength range of 1900 to 3800 mm (same as 10-1 nm) is mainly used, and as the electron beam source, cockroft Walton type, bande graft type, resonant transformer type, insulating core Various types of electron beam accelerators such as a transformer type, a linear type, a dynamitron type, and a high-frequency type lamp can be used to irradiate electrons having energy of 50 to 1000 keV, preferably 100 to 300 keV.

  Examples of the ionizing radiation curable resin include a monomer having a radically polymerizable unsaturated group such as (meth) acryloyl group, (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.

  The ionizing radiation curable resin is sufficiently cured when irradiated with an electron beam, but a photopolymerization initiator is added as a sensitizer when cured by irradiation with ultraviolet rays. The addition amount of the photopolymerization initiator is generally about 0.1 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.

  In addition to improving surface physical properties such as scratch resistance, the surface protective layer can also be adjusted in gloss by adding a known matting agent such as silica, or can impart design properties such as a feeling of painting. . In addition, the surface protective layer can be formed by adding an ultraviolet absorber or a light stabilizer as necessary in order to impart better weather resistance or light resistance. As such an ultraviolet absorber, organic substances such as benzotriazole, benzophenone and salicylic acid ester, or inorganic substances such as fine particles of zinc oxide having a diameter of 0.2 μm or less, cerium oxide and titanium oxide can be used. As the light stabilizer, hindered amine radical scavengers such as bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, radical scavengers such as piperidine radical scavengers, and the like can be used. These ultraviolet absorbers and light stabilizers are usually added so as to be about 0.5 to 10% by mass, but it is generally preferable to use an ultraviolet absorber and a light stabilizer in combination. As the flame retardant, powders such as aluminum hydroxide and magnesium hydroxide are used. The addition amount of the flame retardant is preferably about 10 to 150 parts by mass with respect to 100 parts by mass of the total amount of the high-density polyethylene and the thermoplastic elastomer.

  The surface protective layer is formed by coating and forming such various coating agents by a known coating method such as a gravure coating method, a reverse roll coating method, a knife coating method, a kiss coating method, and other coating methods. Moreover, it forms by well-known printing methods, such as gravure printing and silk screen printing. The thickness of the formed surface protective layer is preferably about 3 to 40 μm, more preferably 10 to 30 μm.

Surface Primer Layer In the building material sheet of the present invention, a primer layer (referred to as a surface primer layer) is preferably provided between the transparent resin layer and the surface protective layer. A surface primer layer has a role which improves the adhesiveness of a transparent resin layer and a surface protective layer. In particular, it is preferably applied when the surface protective layer is formed of a solvent-free active energy ray-curable resin, and has an effect of absorbing shrinkage (followability) when the surface protective layer is cured with active energy rays. As a result, it is possible to solve the problem of delamination based on the strain generated when the surface protective layer is cured, and to improve the adhesion between the transparent resin layer and the surface protective layer.

  In addition, the surface primer layer is formed by coating or the like using a water-based coating agent for the purpose of suppressing the generation of organic volatile substances and improving the working environment at the manufacturing site and the safety in the living space. preferable. As the aqueous coating agent for forming the surface primer layer, in the same manner as the aqueous coating agent suitably used for forming the ink layer described above, an aqueous polyurethane resin, acrylic resin, urethane acrylic resin, polyester resin, polyamide resin, Uses amine-based resins, phenol-based resins, etc., and colorants, dispersants, antifoaming agents, leveling agents, stabilizers, fillers, lubricants, lubricants, antioxidants, UV absorbers, light stabilizers, etc. These additives can be optionally added, and a water solvent or a mixed solvent composed of water and alcohol can be used and mixed well with a mixer or the like.

Back surface primer layer A back surface primer layer is formed in the back surface side of a base material for the purpose of making it easy to adhere the sheet | seat for building materials of this invention to various adherends. Acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, chlorinated polyethylene, etc. are used to form the back surface primer layer, and the ink layer and adhesive layer described above are formed. From the viewpoint of environmental safety, it is preferable to use a water-based coating agent that is preferably employed.

Building material sheet The building material sheet of the present invention having at least a base material, an ink layer, an adhesive layer, and a transparent resin layer, and having a building material sheet configuration in which the respective layers are sequentially laminated, It is used by being laminated on the adherend (backing material).

  As the adherend, a three-dimensional article 41 as shown in FIG. 4, an article of various shapes such as a flat plate 51 and a curved board 51, a sheet (or film), etc. as shown in FIG. 5 are targeted. Such adherends include wood boards such as wood veneer, wood plywood, particle board, medium density fiber board (MDF), wood boards such as wood fiber board, metals such as iron and aluminum, 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, asbestos, titanium Nonwoven fabrics or woven fabrics made of fibers of potassium acid, glass, synthetic resin, etc. can be mentioned.

  In the relationship between the building material sheet 1 and the adherend, if the base material 2 or the back surface primer layer 6 of the building material sheet 1 can be directly bonded to the adherend by heat fusion or the like, the building material sheet 1 And the adherend can be laminated without using an adhesive, but depending on the type of the base material 2 or the back surface primer layer 6 of the building material sheet 1, it cannot be directly bonded to the adherend 15 by heat fusion or the like. Are laminated using a suitable adhesive. In addition, as an adhesive agent, adhesive agents, such as a vinyl acetate type and a urea type, can be mentioned as an example.

  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., the building material sheet 1 is inserted between both male and female molds for injection molding, both molds are closed, the molten resin is injected and filled from the male mold gate, and then cooled. Simultaneous molding of resin molded product and simultaneous injection molding laminating sheet 1 for building material on the surface, (c) Adhesion as described in JP-B-56-45768, JP-B-60-58014, etc. A vacuum press laminating method in which the building material sheet 1 is made to face the surface of the molded product through an agent, and the building material sheet 1 is laminated on the molded product surface by a pressure difference due to vacuum suction from the molded product side, (d) No. 5895, Japanese Patent Publication 3- As described in Japanese Laid-Open Patent Publication No. 666, etc., while supplying the building material sheet 1 via an adhesive in the long axis direction of a columnar adherend such as a cylinder or a polygonal column, a plurality of rollers with different directions are used. A wrapping method or the like in which the building material sheet 1 is sequentially pressure-bonded and laminated on a plurality of side surfaces constituting the body.

  The various adherends on which the building material sheets 1 of the present invention are laminated can be used as various decorative materials and the like by performing a predetermined molding process or the like. For example, interior decorations of buildings such as walls, ceilings, floors, surface decorations of furniture such as window frames, doors, handrails, surface decorations of furniture or cabinets of electrical appliances and OA equipment, vehicle interiors of automobiles, trains, etc. Applications such as cosmetics for window glass are mentioned.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, the unit of the compounding ratio described below is a mass part in principle.

Manufacturing method of polyester polyol (PE-1 and PE-2) A stirring blade and a nitrogen introducing tube are attached to a flask, charged with the raw materials described in i) and ii) below, and stirred at an internal temperature of 150 ° C to 250 ° C. And dehydrated. When the acid value reached 10 mgKOH / g, nitrogen gas was introduced, and the introduction of nitrogen gas was continued until the acid value reached 2 mgKOH / g. Next, using a vacuum pump, the pressure was reduced at 15 Torr for 1 hour to obtain the desired polyester polyols (PE-1) and (PE-2). The acid value and hydroxyl value of the obtained polyester polyols (PE-1) and (PE-2) are shown in the lower part of the raw materials.

i) Raw material of polyester polyol (PE-1), blending ratio, acid value, hydroxyl value ethylene glycol 60.1
Neopentyl glycol 201.7
1,6-hexanediol 171.7
Adipic acid 566.5
Acid value 0.2mgKOH / g
Hydroxyl value 52.0mgKOH / g

ii) Raw material of polyester polyol (PE-2), blending ratio, acid value, hydroxyl value ethylene glycol 40.7
Neopentyl glycol 136.7
1,6-hexanediol 232.6
Adipic acid 191.8
Sebacic acid 398.2
Acid value 0.2mgKOH / g
Hydroxyl value 53mgKOH / g

Production Method of Carboxyl Group-Containing Polyurethane Polyol (a) A stirring blade and a nitrogen introduction tube are attached to a flask, and the polyester polyol (PE-1) or ( PE-2) and dimethylolbutanoic acid were added and melted, and then reacted with isophorone diisocyanate at 80 ° C. with stirring. It was confirmed by IR spectrum that the absorption at 2270 cm −1 was no longer decreased. Of resin was obtained. Subsequently, the same mole of glycol as the remaining isocyanate group was added to obtain a carboxyl group-containing polyurethane polyol (a) -1 to 6 having a terminal hydroxyl group. The following abbreviations are as follows. “Example” and “Comparative Example” shown in Table 1 mean “used in Examples” and “used in Comparative Examples”, respectively.

PE: Polyester polyol 1,6-HDO: 1,6-hexanediol 1,4-BDO: 1,4-butanediol EG: ethylene glycol NPG: neopentyl glycol KOH: potassium hydroxide

Method for producing neutralized product of carboxyl group-containing polyurethane polyol (a) The carboxyl group-containing polyurethane polyol (a) -1 to 6 obtained in the above step is added with 30% potassium hydroxide (KOH) aqueous solution or ethanolamine. To neutralize each. The amount of the base to be neutralized is a polyester polyisocyanate added to the polyester polyisocyanate (b) by adding an amount that neutralizes the acid value of the carboxyl group-containing polyurethane polyol (a) -1 to 100%. The amount necessary to neutralize the acid value of (b) by 100% is obtained by adding a base in an amount that neutralizes the acid value of polyester polyisocyanate (b) to the water used in the water emulsification step. It was. Each neutralized product of the carboxyl group-containing polyurethane polyols (a) -1 to 6 (a) -1K, (a) -1N, (a) -2K, (a) -2N, (a) -3K, (a ) -4K, (a) -1T, (a) -2T, (a) -5K, (a) -6K, the type of carboxyl group-containing polyurethane polyol (a) and the type of neutralizing agent Is shown in Table 2. “Example” and “Comparative example” shown in Table 2 mean “used in the example” and “used in the comparative example”, respectively.

Production method of polyester polyisocyanate (b) Agitating blade and nitrogen introduction tube were attached to a flask, and the polyester polyol (PE-1) or (PE-) obtained in the above step was adjusted so that the acid value and NCO% shown in Table 3 were obtained. 2) and dimethylolbutanoic acid were added and melted, and then isophorone diisocyanate was reacted at 80 ° C. with stirring. It was confirmed by IR spectrum that the absorption at 2270 cm ⁻¹ was no longer decreased. (B) Resin having terminal isocyanate groups of -1 to 4 and polyester polyisocyanate (b) -5 to 6 of Comparative Examples were obtained. Table 3 shows the types of polyester polyol (PE) used for the production of polyester polyisocyanate (b) -1-6. “Example” and “Comparative Example” shown in Table 3 mean “used in Examples” and “used in Comparative Examples”, respectively.

Method for producing water-based polyester polyurethane resin (1) and method for producing curable resin composition (3 ) A neutralized product of the carboxyl group-containing polyurethane polyol (a) obtained in the above step in the first continuous homogenizer ( a) -1K, (a) -1N, (a) -2K, (a) -2N, (a) -3K, (a) -4K, (a) -1T, (a) -2T, (a) -5K, (a) -6K and polyester polyisocyanate (b) -1 to 6 are mixed in the combinations shown in Table 4 so as to have the mass ratio of (a) / (b) shown in Table 4, and then In a second continuous homogenizer, potassium hydroxide or ethanolamine in an amount neutralizing 100% of the acid value of the polyester polyisocyanate (b) in advance with respect to 400 parts by mass of (a) + (b) Add 600 parts by weight of water to which To obtain an emulsion solution. After stirring this for 15 minutes, a 40% aqueous solution of ethylenediamine was added dropwise over 10 minutes as polyamine (c). Next, a 40% aqueous solution of ethanolamine in the same mole as the remaining NCO is added, and the aqueous polyester polyurethane resin (1) -1 to 10 used in Examples for the purpose of hydroxyl value shown in Table 4 is used in Comparative Examples. Aqueous polyester polyurethane resins (1) -11 to 17, 19 were obtained.
In addition, as water-based polyester polyurethane resin (1) -18 used for a comparative example, (a) -1 and (b) -1 which are not neutralized are mixed in a first continuous homogenizer, and the second continuous In a type homogenizer, 400 parts by mass of unneutralized (a) + (b) and 600 parts by mass of an aqueous solution containing potassium hydroxide in an amount to neutralize the acid value thereof are mixed to form an aqueous polyester polyurethane. A resin was obtained.
Table 4 shows the acid value and hydroxyl value of each aqueous polyester polyurethane resin obtained. “Example” and “Comparative Example” shown in Table 4 mean “used in Examples” and “used in Comparative Examples”, respectively.

  Various blending mass ratios of the aqueous resin (1) and the curing agent (2) shown in Table 5 for the curable resin composition (3) obtained by blending the various aqueous resins (1) and the curing agent (2) obtained in the above step. It was made with. The curing agent (2) used was Nippon Polyurethane Industry Co., Ltd. (Aquanate 130; NCO% = 16.4, average functional group number 4.6). The blending mass is shown as a resin solid content ratio. “Example” and “Comparative example” shown in Table 5 mean “used in the example” and “used in the comparative example”, respectively.

Fabrication of sheet for building material A gravure plate with a line number of 54 lines / inch and a plate depth of 40 μm is printed on the surface so that the coating amount is 3 g / m ² and the back surface has a line number of 70 lines / inch. The curable resin composition is formed on the surface side of a polypropylene resin film, using a gravure plate having a plate depth of 40 μm and having a back surface primer (two-component curable polyester urethane resin) applied to a coating amount of 2 g / m ^2. After coating the products (3) -1 to 10 and (3) -11 to 19 (excluding (3) -15 and (3) -18) and passing through a drying step, the maleic acid-modified propylene resin is used. The phenolic antioxidant 0.2 mass%, the hindered amine stabilizer 0.3 mass%, and the anti-blocking agent 0.2 mass% were added to the first layer having a thickness of 10 μm and the random copolymer polypropylene, respectively. Tree The second layer having a thickness of 70 μm is coextruded under ozone irradiation at 180 ° C. to form a transparent resin layer 5 of about 80 μm, and laminated so that the adhesive layer side is in contact with the maleic acid-modified polypropylene layer. . Thereafter, the transparent resin layer is embossed and a surface protective layer (two-component curable polyester urethane resin) is applied using a gravure plate having a line number of 54 lines / inch and a plate depth of 40 μm so that the coating amount is 3 g / m ^2. It coated and obtained the sheet | seat for building materials of Examples 1-10 and Comparative Examples 11-19.

  Various types of water-based polyester polyurethane resin (1) in curable resin composition (3), each kind of terminal hydroxyl group, neutralizing agent, polyisocyanate type, carboxyl group-containing polyurethane polyol (a) and polyester polyisocyanate Table 6 shows the blending ratio (a / b), acid value, and hydroxyl value of (b). Table 6 shows the mass ratio of the water-based polyester polyurethane resin (1) and the curing agent (2).

  With respect to the building material sheets obtained in Examples 1-10 and Comparative Examples 11-19, the properties of the building material sheets were evaluated by the following tests (1) to (6).

(1) Normal interlayer adhesion test Using a tensile tester (INSTRON 5500: trade name, manufactured by INSTRON), a tensile test was performed under the conditions of a 25 ° C tensile speed of 100 mm / min and a sample width of 1 inch (2.54 cm). The tensile strength was evaluated by the strength when a tensile test was performed under the condition of an opening angle of 180 ° between the base material of the building material sheet and the transparent resin layer. When the peel strength is 19.6N or higher, the pass is ◎, when 15.0N or higher and lower than 19.6 is passed, the pass is ◯, 10.0N or higher and lower than 15.0N is rejected. Those less than N were shown as x as rejects.

(2) Weather resistance acceleration test Using an i-super UV tester (trade name, manufactured by Iwasaki Electric Co., Ltd.), ultraviolet rays having an illuminance of 60 mW / cm 2, a distance from the light source of 240 mm, and an irradiation spectrum band of 295 to 450 mm are applied to the building material sheet. The surface protective layer side was irradiated for 20 hours (black panel temperature 63 ° C., humidity 50%) and tested in 4 cycles (96 hours) under a cycle condition of 4 hours in the dark (black panel temperature 30 ° C., humidity 98%). (Hereinafter referred to as a weather resistance acceleration test). After the test, a sheet sample for building materials was taken out and left at room temperature 25 ° C./humidity 50% for 2 hours, then, using a tensile testing machine (INSTRON 5500: trade name, manufactured by INSTRON), 25 ° C., tensile speed 100 mm / A tensile test was performed under the condition of minutes to evaluate the peel strength. A peel strength of 8N or more and less than 10N was regarded as acceptable, a case of 5N or more and less than 8N was rejected, and a case of less than 5N was regarded as unacceptable.

(3) Water-resistant interlayer adhesion test The building material sheet was immersed in water for 4 weeks. After the test, a building material sheet sample was taken out and subjected to a tensile test under conditions of room temperature of 25 ° C. and a tensile speed of 100 mm / min to evaluate the peel strength. A case where the peel strength is 15.0 N or more is acceptable, and a case where the peel strength is 10.0 N or more and less than 15.0 N is acceptable. Those less than N were rejected, and those less than 5N were rejected, respectively.

(4) Humidity-resistant interlayer adhesion test The building material sheet was placed in a constant temperature / humidity bath at 60 ° C / 90% and left for 1 month. After the test, the building material sheet sample was taken out, tested at room temperature 25 ° C./humidity 50%, and allowed to stand for 2 days. Then, using a tensile tester (INSTRON 5500: trade name, manufactured by INSTRON), 25 ° C., tensile speed 100 mm. A tensile test was performed under the conditions of / min and the peel strength was evaluated. A peel strength of 10N or more was evaluated as “◎”, 8N or more and less than 10N as “good”, “5” or more and less than 8N as “good”, and less than 5N as “bad”.

(5) Heat-resistant interlayer adhesion test The building material sheet was placed in a thermostat at a temperature of 80 ° C and left for 1 month. After the test, a sample of the building material sheet was taken out, tested at room temperature of 25 ° C./humidity of 50%, and allowed to stand for 2 days. Then, using a tensile tester (INSTRON 5500: trade name, manufactured by INSTRON), 25 ° C., tensile speed A tensile test was performed under the condition of 100 mm / min to evaluate the peel strength. A peel strength of 15N or more was expressed as 合格, and 12N or more and less than 15N was marked with ◯, 10N or more and less than 12N was marked as △, and less than 10N was rejected.

(6) Sensory test The odor after laminating the transparent resin layer was evaluated sensorily and evaluated with two types of “I don't care” and “I had a bad odor”.

  As described above, the water-based polyester polyurethane resin (1) according to each of the above examples is a highly practical one that can be stably produced even in the absence of volatile amines and reduction of organic solvents. The film laminated with the curable resin composition (3) obtained by blending (2) not only solves the odor problem but also is hardly affected by ultraviolet rays, humidity, and temperature, and has excellent weather resistance. Is expressed.

  The sheet for building materials of the present invention has a polyester urethane-based adhesive layer formed using a water-based adhesive, and therefore has excellent environmental safety and interlayer adhesion, and is used for interior decoration of buildings, surface decoration of fittings, and interior decoration of vehicles. Used for etc.

It is sectional drawing which shows an example of the simplest layer structure of the sheet | seat for building materials of this invention. It is sectional drawing which shows one example of the general layer structure of the sheet | seat for building materials of this invention. It is sectional drawing which shows another example of the general layer structure of the sheet | seat for building materials of this invention. It is sectional drawing which shows one example which laminated | stacked the sheet | seat for building materials of this invention on the to-be-adhered body (backing material) which is a three-dimensional shaped article. It is sectional drawing which shows one example which laminated | stacked the sheet | seat for building materials of this invention on plate | board materials or sheets (or films), such as flat form and curved surface form.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 11, 21 Building material sheet 2 Base material 3 Ink layer 4 Adhesive layer 5 Transparent resin layer 6 Back surface primer layer 7 Surface protective layer 8 Concavity and convexity 9 Surface primer layer 41 Three-dimensional shaped article 51 Board material

Claims (10)

At least a base material and a transparent resin layer are laminated for a building material sheet via an adhesive layer, and the adhesive layer is
Aqueous polyester polyurethane resin (1) obtained by reaction with polyester polyisocyanate (b) and polyamine (c) in the presence of a neutralized product of carboxyl group-containing polyurethane polyol (a), and polyisocyanate ( 2) and
It is formed using the curable resin composition (3) containing this, The sheet | seat for building materials characterized by the above-mentioned.   2. The building material according to claim 1, wherein the carboxyl group of the carboxyl group-containing polyurethane polyol (a) is neutralized with any one of alkali metal ions selected from lithium ions, sodium ions, and potassium ions. Sheet.   The building material sheet according to claim 1, wherein the carboxyl group of the carboxyl group-containing polyurethane polyol (a) is neutralized with a primary or secondary amine.   4. The building material according to claim 1, wherein the carboxyl group-containing polyurethane polyol (a) has an acid value of 30 to 60 mg KOH / g and a hydroxyl value of 10 to 60 mg KOH / g. 5. Sheet.   The terminal of the carboxyl group-containing polyurethane polyol (a) is a hydroxyl group modified with any one selected from 1,4-butanediol, diethylene glycol, and 1,6-hexanediol. The sheet | seat for building materials of any one of thru | or 4.   The building material sheet according to any one of claims 1 to 5, wherein the polyester polyisocyanate (b) has an acid value of 0 to 12 mgKOH / g.   The blending ratio of the carboxyl group-containing polyurethane polyol (a) and the polyester polyisocyanate (b) is (a) :( b) = 10: 90 to 50: 50% by mass. 6. The building material sheet according to any one of 6 above.   8. The building material sheet according to claim 1, wherein the building material sheet is a building material sheet having at least a base material, an ink layer, an adhesive layer, and a transparent resin layer, and the layers are sequentially laminated. The sheet | seat for building materials as described in a term. In the presence of a neutralized product obtained by neutralizing the carboxyl group of the carboxyl group-containing polyurethane polyol (a) with any of alkali metal ions selected from lithium ions, sodium ions, and potassium ions, or primary or 2 An aqueous polyester polyurethane resin (1) comprising a high molecular weight product of polyester polyurethane polyurea by reaction with polyester polyisocyanate (b) and polyamine (c) in the presence of a neutralized product neutralized with a grade amine. Obtaining step (A);
A step (B) of obtaining a curable resin composition (3) by blending the polyisocyanate (2) with the aqueous polyester polyurethane resin (1) obtained by the step (A);
Step (C) of laminating at least the base material and the transparent resin layer using the curable resin composition (3) obtained in the step (B),
A method for producing a sheet for building materials. An aqueous polyester polyurethane resin (1) comprising a high molecular weight product of polyester polyurethane polyurea by reaction with polyester polyisocyanate (b) and polyamine (c) in the presence of a neutralized product of the carboxyl group-containing polyurethane polyol (a). How to get
The neutralized product of the carboxyl group-containing polyurethane polyol (a) and the polyester polyisocyanate (b) are mixed, and water is further mixed to obtain an emulsion.
The manufacturing method of the sheet | seat for building materials of Claim 9 which mixes a polyamine with the obtained emulsion and makes it chain-extend.

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