JP2012021103A - Resin composition, and laminate and image-formed material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which is excellent in designabilty, is easily unified with an adherend by heating when being pasted on the adherend, is firmly fixed to an adherend, can easily be peeled off when being peeled off, and from which dirts such as dusts can simply be removed with water or soap water when the dirts are attached.SOLUTION: The resin composition includes a styrenic block copolymer (A), a mineral oil softener (B), a tackifier resin (C), and a colorant (D), wherein the styrenic block copolymer (A) has a styrene ratio of 10 to 40 wt.%, and has a triblock structure; the mineral oil softener (B) has a weight-average molecular weight of 700 to 10,000; the tackifier resin (C) has a softening point of 80°C to 160°C. The resin composition is prepared by blending 3 to 65 pts.wt of the styrenic block copolymer (A), 10 to 95.9 pts.wt of the mineral oil softener (B), 1 to 50 pts.wt of the tackifier resin (C), and 0.1 to 10 pts.wt of the colorant (D) so that the total thereof becomes 100 pts.wt.

Description

  The present invention relates to a resin composition that can be applied and pasted in an arbitrary shape, a laminate using the resin composition, and an image-formed product on which a decorative object is adhered. Specifically, the present invention relates to a resin composition suitably used as a design material, a laminate using the resin composition, and an image formed product.

  In recent years, there has been a demand for product design in order to increase the added value of products, and among them, the demand for higher design of products is the highest. In vehicles, buildings, traffic signs, packaging materials, signboards, etc., an adhesive member for a design in which an adhesive layer is provided on a sheet substrate is used. There are those provided with a non-colored pressure-sensitive adhesive layer, or those provided with a pressure-sensitive adhesive layer imparted with design properties by coloring or the like on a transparent sheet.

  As pressure-sensitive adhesives with design properties, carboxyl-containing (meth) acrylic polymers, pigments or dyes, and acrylic colored pressure-sensitive adhesives containing amino group-containing (meth) acrylic polymers that do not contain aromatic vinyl monomers are known. (See Patent Document 1).

  A white toner containing a white pigment and a polyester plasticizer having a glass transition temperature of −10 ° C. or lower and a white pressure-sensitive adhesive composition containing the white toner are known (see Patent Document 2).

  Also, a black heat comprising ethylene / α-olefin copolymer rubber, mineral oil softener, α-olefin crystalline polymer, α-olefin amorphous polymer, weathering agent, and carbon black. A plastic elastomer composition is known (see Patent Document 3).

  The colored pressure-sensitive adhesive described in Patent Document 1 is easy to peel off and has good adhesion and coating appearance, but since it is manufactured using a solvent, the solvent must be volatilized and removed in the coating process. In addition, the volatilized solvent causes environmental pollution and is not preferable from the viewpoint of the environment. In addition, since a crosslinking agent is used, it cannot be used until the crosslinking is completed because a sufficient function that the crosslinking is expected to be incomplete cannot be exhibited.

  The white pressure-sensitive adhesive composition described in Patent Document 2 is sufficiently satisfactory to freely express a desired color, texture, or design that has been emphasized in recent years. Has become shorter and does not fully meet the demand for easy stripping even without a skilled worker.

  The black thermoplastic elastomer composition described in Patent Document 3 has excellent weather resistance and can be recycled. However, if the black thermoplastic elastomer composition is affixed to a wall, wood product, marble, etc. and peeled off, the color will transfer, and if the black thermoplastic elastomer composition is left in contact with a polyolefin resin, etc. Color transfer was observed in polyolefin resin and the like. Furthermore, when it was affixed and peeled off to glass, the oil component had adhered to glass.

JP 2008-308646 A JP 2004-51753 A JP 2006-57016 A

  The object of the present invention is excellent in design, is easily integrated by heating when affixed to an adherend, and is firmly fixed to the adherend and easily peeled off when peeled off. An object of the present invention is to provide a resin composition that can be easily removed with water or soapy water when dust such as dust adheres, a laminate using the resin composition, and an image formed product. .

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention is a resin composition comprising a styrenic block copolymer (A), a mineral oil softener (B), a tackifier resin (C) and a colorant (D),
The styrene block copolymer (A) has a styrene ratio of 10 to 40% by weight, and has a triblock structure.
The mineral oil softener (B) has a weight average molecular weight of 700 to 10,000.
The tackifying resin (C) has a softening point of 80 to 160 ° C.,
Styrenic block copolymer (A) 3 to 65 parts by weight, mineral oil softener (B) 10 to 95.9 parts by weight, tackifier resin (C) 1 to 50 parts by weight and colorant (D) 0.1 The present invention relates to a resin composition comprising 10 parts by weight to 10 parts by weight so that the total is 100 parts by weight.

  Moreover, this invention relates to the resin composition of the said invention characterized by the viscosity in 170 degreeC being 500-50000 mPa * s.

  Moreover, this invention relates to the laminated body formed by laminating | stacking the resin composition layer formed from the resin composition of one of the said invention on the single side | surface or both surfaces of a sheet-like base material.

Moreover, this invention relates to the laminated body of the said invention characterized by the application quantity of a resin composition layer being 1-1000 g / m < ² >.

  The present invention also relates to an image formed product obtained by processing the resin composition of any one of the above inventions.

  The present invention also relates to an image formed product obtained by processing the laminate of any one of the above inventions.

  According to the present invention, it is excellent in design, is easily integrated by heating when affixed to an adherend, further firmly fixed to the adherend, and can be easily peeled off when peeled off, When dust such as dust adheres, it has become possible to provide a resin composition that can be easily removed with water or soapy water, and a laminate and an image formed product using the resin composition. Furthermore, a laminate in which the resin composition layer is laminated on one side or both sides can be stored without the resin composition layer protruding from the end portion over time.

The resin composition of the present invention will be described.
The resin composition of the present invention comprises a styrenic block copolymer (A), a mineral oil softener (B), a tackifier resin (C), a colorant (D), and other additives as necessary. It is a resin composition formed by blending.

The styrene block copolymer (A) constituting the resin composition used in the present invention is a styrene-butadiene-styrene block copolymer (hereinafter also abbreviated as “SBS”), a styrene-butadiene-styrene block copolymer. Hydrogenated product (hereinafter abbreviated as “SEBS”), styrene-isoprene-styrene block copolymer (hereinafter also abbreviated as “SIS”), hydrogenated product of styrene-isoprene-styrene block copolymer ( Hereinafter, abbreviated as “SEPS”), styrene-butadiene-isoprene-styrene block copolymer (hereinafter also abbreviated as “SBIS”), hydrogenated product of styrene-butadiene-isoprene-styrene block copolymer (hereinafter referred to as “SBIS”). At least one selected from the group consisting of “abbreviated as“ SEEPS ””.
Further, the copolymer may be carboxyl-modified, and further, the styrene block in the copolymer is a mixture of styrene and other aromatic vinyl compounds such as α-methylstyrene. A copolymer may be included.
Furthermore, the styrene-based block copolymer (A) has a styrene ratio of 10 to 40% by weight and has a triblock structure, but only has a triblock structure. Is not limited, and a part of the structure may have a diblock structure. The diblock type content is preferably 60% by weight or less, and more preferably 50% by weight or less. If it exceeds 60% by weight, the cohesive force is lowered.
These are preferable because they are excellent in heat resistance during melting.
The styrenic block copolymer (A) may be used alone or in combination of two or more.

  When the total of the styrenic block copolymer (A), the mineral oil softener (B), the tackifier resin (C), and the colorant (D) constituting the resin composition of the present invention is 100 parts by weight, the resin The compounding quantity of the styrenic block copolymer (A) used for a composition is 3-65 weight part. Preferably it is 5-60 weight part. When the blending amount of the styrenic block copolymer (A) is less than 3 parts by weight, the cohesive force of the resulting resin composition tends to decrease. When the blending amount of the styrenic block copolymer (A) exceeds 65 parts by weight, production by kneading may be difficult.

  The mineral oil softener (B) constituting the resin composition used in the present invention is a mixture of aromatic hydrocarbons, hydrocarbons containing naphthenic rings, and paraffin chains, and the total number of carbon atoms in the paraffin chains. Paraffinic mineral oil softeners accounting for 50% or more of the number are preferred. Generally, paraffin-based mineral oil softeners whose paraffin chain carbon number occupies 50% or more of the total carbon number, those whose naphthenic ring carbon number occupies 30 to 40% of the total carbon number, naphthenic mineral oil softener, aromatic A group whose carbon number accounts for 30% or more of the total carbon number is called an aromatic mineral oil softener and is distinguished.

  The weight average molecular weight in terms of polystyrene by the gel permeation chromatography method (hereinafter also abbreviated as “GPC”) of the mineral oil softener (B) constituting the resin composition used in the present invention is 700 to 10,000. Preferably it is 800-9500. If the mineral oil softening agent (B) has a weight average molecular weight of less than 700, bleeding out tends to occur. If the weight average molecular weight of the mineral oil softening agent (B) exceeds 10,000, the fluidity at the time of melting tends to decrease.

  The resin composition of the present invention is not used at all in the case of a general resin composition, or even if used, a mineral oil softening that is used in a very small amount in order to improve processability and improve adhesion It is important to add a relatively large amount of the agent (B). That is, the resin composition has specific elasticity by controlling the ratio of the styrenic block copolymer (A) and the mineral oil softener (B). Also, the butadiene and isoprene sites of the styrene-based block copolymer (A) in which the bleed-out of the mineral oil softener (B) (contamination to the adherend) is similar in structure to the mineral oil softener (B) It becomes possible to suppress it by adapting to styrene and physically cross-linking the styrene part of the styrenic block copolymer (A).

  When the total of the styrenic block copolymer (A), mineral oil softener (B), tackifying resin (C), and colorant (D) constituting the resin composition of the present invention is 100 parts by weight, the resin The compounding quantity of the mineral oil softener (B) used for a composition is 10-95.9 weight part. Preferably it is 15-90 weight part. If the blending amount of the mineral oil softening agent (B) is less than 10 parts by weight, the processability is deteriorated. When the blending amount of the mineral oil softener (B) exceeds 95.9 parts by weight, it becomes difficult to maintain the cohesive strength.

  As the tackifier resin (C) constituting the resin composition used in the present invention, hydrogenated aliphatic, alicyclic and aromatic petroleum resins and terpene resins are suitable for weather resistance. Since it is excellent, it is preferable. Tackifying resin (C) may be used independently, or 2 or more types may be used together.

The softening point of the tackifier resin (C) is preferably 80 to 160 ° C. When the softening point of the tackifier resin (C) is less than 80 ° C., the cohesive force is lowered, and the cohesive failure may occur at the time of peeling. When the softening point of the tackifying resin (C) exceeds 160 ° C., tack may disappear in a low temperature range.
In addition, the softening point in this invention is the temperature calculated | required by the method prescribed | regulated to JISK6863. That is, after leaving the specified ring filled with the resin composition to stand for 12 hours or more, it is placed in a heating medium and the specified sphere is placed on the specified ring filled with the resin composition and heated at a constant rate. When the temperature of the medium is raised, the temperature is when the sphere sinks due to softening of the resin composition and touches the bottom plate of the ring platform.

  When the total of the styrenic block copolymer (A), mineral oil softener (B), tackifying resin (C), and colorant (D) constituting the resin composition of the present invention is 100 parts by weight, the resin The compounding quantity of tackifying resin (C) used for a composition is 1-50 weight part. Preferably it is 3-45 weight part. If the compounding amount of the tackifier resin (C) is less than 1 part by weight, the processability is deteriorated. When the amount of the tackifier resin (C) exceeds 50 parts by weight, tack may disappear in a low temperature range.

As the colorant (D) constituting the resin composition used in the present invention, a dye, a dye and a pigment are preferable. As the coloring matter, dye, and pigment, brown 201, black 401, purple 201, purple 401, blue 1, blue 2, blue 201, blue 202, blue 203, blue 204, blue 205 No., Blue 403, Blue 404, Green 201, Green 202, Green 204, Green 205, Green 3, Green 401, Green 402, Red 102, Red 104-1, Red 105 -1, Red 106, Red 2, Red 201, Red 202, Red 203, Red 204, Red 205, Red 206, Red 207, Red 208, Red 213, Red 214 No., Red 215, Red 218, Red 219, Red 220, Red 221, Red 223, Red 225, Red 226, Red 227, Red 228, Red 230-1, Color No. 230-2, Red No. 231, Red No. 232, Red No. 3, Red No. 401, Red No. 404, Red No. 405, Red No. 501, Red No. 502, Red No. 503, Red No. 504, Red No. 505, Red No. 506, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 205, Orange No. 206, Orange No. 207, Orange No. 401, Orange No. 402, Orange No. 403, Yellow No. 201, Yellow No. 202-1, Yellow 202-2, Yellow 203, Yellow 204, Yellow 205, Yellow 4, Yellow 401, Yellow 402, Yellow 403-1, Yellow 404, Yellow 405, Yellow 406, Yellow 407 No., legal dyes such as Yellow 5, other acidic dyes such as Acid Red 14, basic dyes such as Arianor Sienna Brown, Arianor Madder Red, Arianor Steel Blue, Arianor Straw Yellow, HC Yellow 2, HC Yellow 5, HC Red 3 , 4-hydoxypropyl amino-3-nitrophenol,
N, N'-bis (2-hydroxyethyl) -2-nitro-p-phenylenediamine, nitro dyes such as HC Blue 2 and Basic Blue 26, inorganic white pigments such as titanium dioxide and zinc oxide, iron oxide (Bengara), titanium Inorganic red pigments such as iron oxide, inorganic brown pigments such as γ-iron oxide, inorganic yellow pigments such as yellow iron oxide and loess, inorganic black pigments such as black iron oxide and low-order titanium oxide, mango violet, Inorganic purple pigments such as cobalt violet, inorganic green pigments such as chromium oxide, chromium hydroxide and cobalt titanate, inorganic blue pigments such as ultramarine and bitumen, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide Coated talc, colored titanium oxide coated mica, bismuth oxychloride, pearl pigment such as fish scale foil, metal powder pigment such as aluminum powder, copper powder, gold, surface treatment inorganic and metal Powder pigment, red 201, red 202, red 204, red 205, red 220, red 226, red 228, red 405, orange 203, orange 204, yellow 205, yellow 401 , Blue 404, Red 3, Red 104, Red 106, Red 227, Red 230, Red 401, Red 505, Orange 205, Yellow 4, Yellow 5, Yellow 202, Yellow Organic pigments such as zirconium, barium or aluminum lakes such as No. 203, Green No. 3, Blue No. 1, etc., carbon black pigments, surface treatment organic pigments, azo, ansanthrone, anthrapyrimidine, anthraquinone, isoindolinone , Isoindoline, indanthrone, quinacridone, quinophthalone, dioxazine, diketopyrrolopyrrole, thia Organic pigments such as Nindigo, Thioindigo, Pyranthrone, Flavanthrone, Perinone, Perylene, and Benzimidazolone, Anthraquinones such as Astaxanthin and Alizarin, Anthocyanidin, β-Carotene, Catenal, Capsanthin, Chalcone, Calsamine Natural pigments / dyes such as quercetin, crocin, chlorophyll, curcumin, cochineal, shikonin, naphthoquinones, bixins, flavones, betacyanidine, henna, hemoglobin, lycopene, riboflavin, rutin, p-phenylenediamine, toluene-2, 5-diamine, o-, m-, or p-aminophenol, m-phenylenediamine, 5-amino-2-methylphenol, resorcin, 1-naphthol, 2,6-diaminopyridine and the like Preferred examples include oxidative dye intermediates such as salts and auto-oxidative dyes such as couplers and indolines, and dihydroxyacetone.
Further, processed color materials such as crayons obtained by processing these color materials, oil paints, offset inks, colorants dispersed with oxidized wax, and oil-based dyes can be easily used.

  When the total of the styrenic block copolymer (A), mineral oil softener (B), tackifying resin (C), and colorant (D) constituting the resin composition of the present invention is 100 parts by weight, the resin The compounding quantity of the coloring agent (D) used for a composition is 0.1-10 weight part. Preferably it is 0.3-9.5 weight part. When the blending amount of the colorant (D) is less than 0.1 parts by weight, the concentration is low and no coloring effect is observed. When the blending amount of the colorant (D) exceeds 10 parts by weight, the concentration is too high to obtain a clear color.

  To the resin composition of the present invention, additives such as an antioxidant, an ultraviolet absorber, an antibacterial agent, a deodorant, a fragrance, and an insect repellent may be added as long as the object of the invention is not impaired.

  Examples of the antioxidant include pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionate, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxy Ethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl] propionate, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butyl) Phenyl) pentaerythritol diphosphite, etc. These antioxidants may be used alone or in two kinds. Above may be used in combination.

  The above-mentioned phenolic antioxidant is stabilized by donating hydrogen to ROO (peroxy radical) generated in the chain growth process of auto-oxidation, and becomes a stable phenoxy radical protected by an ortho-position substituent. It functions as a radical trapping agent that stops the chain reaction, thereby effectively suppressing thermal degradation of the resin composition. In particular, a combination of a phenol-based antioxidant and a lactone-based antioxidant, a vitamin E-based antioxidant, or the like, which has a faster radical trapping reaction than the phenol-based antioxidant, can be further improved. In addition, the above phosphorus antioxidants have the function of non-radically decomposing peroxides and ROOH and stopping the chain reaction in the auto-oxidation process, thereby effectively preventing the thermal deterioration of the resin composition. To suppress.

  The ultraviolet absorber is not particularly limited, and examples thereof include commonly used ones such as salicylic acid series, benzophenone series, and benzotriazole series. These ultraviolet absorbers may be used alone or in combination of two or more.

  Examples of the antibacterial agents include benzylamine antibacterial agents such as butenafine and salts thereof, bifonazole, neticoconazole, ketoconazole, lanoconazole, clotrimazole, miconazole, oxyconazole, thioconazole, croconazole, omoconazole, sulconazole and salts thereof Imidazole antibacterial agents, allylamine antibacterial agents such as terbinafine and its salts, morpholine antibacterial agents such as amorolfine and its salts, thiocarbamic acid antibacterial agents such as rilanaphthate, tolnaftate and tosiclate, nystatin, tricomycin, variocin, siccanin, And antibacterial agents such as antibiotics such as pyrrolnitrin. These antibacterial agents may be used alone or in combination of two or more.

  The deodorant is not particularly limited as long as it has a deodorizing effect, but lauryl methacrylate, geranyl chlorinate, citronellyl senecionate, terpene aldehydes, pyruvate esters, zinc 2-ethylhexanoate And zinc ricinoleate. These deodorizers may be used independently and 2 or more types may be used together.

  Examples of the above fragrances include hydrocarbon fragrances such as pinene and limonene, alcoholic fragrances such as linalool, geraniol, citronellol, menthol, borneol, benzyl alcohol, anis alcohol and β-phenethyl alcohol, and phenolic fragrances such as anethole and eugenol. , N-butyraldehyde, isobutyraldehyde, hexylaldehyde, citral, citronellal, benzaldehyde, aldehyde-based fragrances such as cinnamic aldehyde, ketone-based fragrances such as carvone, menthone, camphor, acetophenone, ionone, γ-butyllactone, coumarin, cineol Lactone fragrances such as octyl acetate, benzyl acetate, cinnamyl acetate, butyl propionate, methyl benzoate and the like. These fragrance | flavors may be used independently and 2 or more types may be used together.

  Examples of insect repellents include camphor, naphthalene, paradichlorobenzene, isobornyl, thiocyanoacetic acid, 1,2-benzenedicarboxylic acid diethyl ester, paraform, chlorpicrin, insecticide, empentrin, transfluthrin, allethrin, phenothrin, and eminence. . These insect repellents may be used independently and 2 or more types may be used together.

  The addition amount of additives such as ultraviolet absorbers, antibacterial agents, deodorants, fragrances, and insect repellents that can be added within a range not impairing the object of the present invention is 10% by weight or less in 100% by weight of the resin composition. Preferably, it is 8 wt% or less. If it exceeds 10% by weight, bleeding may occur.

  The method for producing the resin composition of the present invention is not particularly limited, and is a hot melt method in which heating, mixing is performed using a roll, a Banbury mixer, a kneader, a melting kettle equipped with a stirrer, a uniaxial or biaxial extruder, and the like. Any method such as a solvent method dissolving in a suitable solvent can be used, but the hot melt method is preferable because it has a small influence on the environment.

The resin composition of the present invention can be applied at 150 to 180 ° C. in order to prevent deterioration caused by applying excessive heat, and is a roll that requires low-viscosity coating or a stirrer for melting. Can also be used with a melting pot equipped with From such a viewpoint, the resin composition of the present invention preferably has a viscosity at 170 ° C. of 500 to 50000 mPa · s.
When the viscosity at 170 ° C. is less than 500 mPa · s, there is a possibility that the resin composition may sag when the coating amount is increased. When the viscosity at 170 ° C. exceeds 50000 mPa · s, workability may be a problem during coating.
The viscosity of the resin composition is a value measured using a B-type viscometer (measurement conditions are 170 ° C., rotor No. 3, 12 rpm, 30 seconds).

  The resin composition of the present invention is a heat-melted one or a solution thereof, a coating machine or hot-melt coating machine usually used for a sheet-like substrate such as paper or resin, a bar coater, an applicator, a doctor blade, Using a soldering iron, spatula, roller, disposable chopsticks, brush, spatula, cutter, etc., applying in various patterns such as mirror surface state, foamed state, bead state, spiral state, etc., heating and cooling as necessary, A resin composition layer can be formed, and various laminates in which the resin composition layer is laminated can be obtained. The resin composition can be applied in layers, and two kinds of resin compositions can be applied separately in parallel on the same sheet-like substrate.

  Moreover, after providing a resin composition layer on the mold release sheet mentioned later, the laminated body of this invention can also be obtained by bonding the said resin composition layer and a sheet-like base material.

  The resin composition of the present invention is excellent in heat resistance and can be suitably used as a resin composition because the change in melt viscosity with time is small even at a high melting temperature. In forming the resin composition layer, the resin composition is preferably melted by heating and applied onto the substrate.

  The basic constitution of the laminate of the present invention is a single-area layered body such as “sheet-like substrate / resin composition layer / release sheet” or “release sheet / resin composition layer / sheet-like substrate”. It is a double-sided laminate such as “/ resin composition layer / release sheet”. At the time of use, the release sheet is peeled off, and the resin composition layer is attached to the adherend.

  There is no restriction | limiting in particular as a raw material of a sheet-like base material, It can use. As resin sheets, polyester resins, polycarbonate resins, polyarylate resins, acrylic resins, polyphenylene sulfide resins, polystyrene resins, vinyl resins, vinyl chloride resins, polyimide resins, epoxy resins, polyethylene, polypropylene In addition, there are single layers or laminates of polyolefin resins such as Poorinorbornene. In addition, a nonwoven fabric, a woven fabric, a cloth, paper, glass, a seto thing, metal foil, a metal mesh, etc., and the composite containing these are mentioned. Further, if necessary, the surface of the sheet may be subjected to easy adhesion treatment such as corona discharge treatment, plasma treatment, blast treatment, chemical etching treatment, antistatic treatment, coloring treatment and the like.

  Although there is no restriction | limiting in particular in the thickness of these sheet-like base materials, 1-1000 micrometers is preferable from workability | operativity.

The coating amount of the resin composition layer is preferably 1 to 1000 g / m ² , more preferably 5 to 980 g / m ² . If the coating amount of the resin composition layer is less than 1 g / m ² , it is difficult to develop adhesive strength. Even when the coating amount of the resin composition layer exceeds 1000 g / m ² , in particular, improvement in required characteristics cannot be expected in many cases.

  The resin composition layer can be used by being bonded to a release sheet or the like as necessary. The release sheet is not particularly limited as long as the surface is subjected to a release treatment, such as a polyester resin such as polyethylene terephthalate (PET), a polyolefin resin such as polyethylene, polypropylene, polynorbornene, a polyphenylene sulfide resin, The thing which uses as a base material the sheet | seat which consists of triacetylcellulose resin, acrylic resin, etc. is mentioned.

  The laminate of the present invention has either a configuration in which the resin composition layer is sandwiched between the sheet-like base material and the release sheet, or between the sheet-like base material and the sheet-like base material. Also good.

An image-formed product can be obtained by processing the resin composition or laminate of the present invention.
Specific examples of the processing include, for example, heating and melting, forming a step, forming unevenness, and coloring (color mixing). Furthermore, drawing and the like with the resin composition itself is also included in the processing here.
In addition, various decorations may be attached to the image formed product of the present invention.
Examples of the ornament include sequins, fluorescent materials, phosphorescent materials, inorganic powders, plastic beads, glass beads, plated beads, and design cloths. These ornaments may be used alone or in combination of two or more.

The image-formed product of the present invention can be easily attached and produced by placing the decorative product on the surface of the resin composition and melting only the surface of the resin composition by heating.
In addition, the image-formed product of the present invention can be prepared using a resin composition colored in advance, but is dispersed with a crayon processed with a transparent resin composition and a coloring material, oil paint, offset ink, and oxidized wax. It is also possible to produce using a resin composition that is simply produced by heat-melting processed color materials such as colorants and oil-based dyes (heat-melting with a household oven toaster, IHI heater, etc.). Furthermore, these color sheets are arranged side by side to form an image in order to impart design properties, but they can be handled safely because their hands are not stained with color materials and volatile components such as solvents are not used. It is a big feature, and it is also a great feature that it can be attached to stained glass, oil painting, stone (cloisonne ware) and various decorative items. The produced image formed product can be attached to a window glass, a wall, a desk, a pillar, a door, a refrigerator, etc., and can be easily removed if necessary.

EXAMPLES Hereinafter, the present invention will be described specifically and in detail with reference to examples. However, these examples are only one aspect of the present invention, and the present invention is not limited to these examples.
In the examples, “part” means “part by weight” and “%” means “% by weight”.
The weight average molecular weight by GPC in the present invention refers to a polystyrene conversion obtained by flowing a dilute resin solution through a column packed with gel-like particles and measuring different times until it flows out depending on the molecular size. The weight average molecular weight.
Specific measurement conditions are as follows.
Equipment: Prominence manufactured by Shimadzu Corporation
Column: TOSgel TSKgel GMH × 2 connected detector: RID-10A
Solvent: THF (tetrahydrofuran)
Column temperature: 40 ° C
Flow rate: 1 mL / min

(Production Examples 1-6)
In a kneader equipped with a stirrer, the styrene-based block copolymer (A), the tackifier resin (B), the tackifier resin (C), the colorant (D) and, if necessary, the number of parts shown in Table 1 ( Other components other than A), (B), (C), and (D) were added and stirred at 160 ° C. for 3 hours to obtain a resin composition. The obtained resin composition was heated and melted to 160 ° C., poured into a smooth bat heated in advance to 160 ° C. so as to have a weight of 500 g / m ² , and cooled to prepare a resin sheet. Furthermore, a releasable sheet was bonded to both surfaces of this resin sheet.

(Production Example 7)
A monomer comprising 60 parts of methyl methacrylate, 34 parts of butyl methacrylate and 6 parts of N, N-dimethylaminoethyl methacrylate in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, a reflux condenser and a dropping funnel 40 parts of the mixture and 60 parts of ethyl acetate were added, the air in the four-necked flask was replaced with nitrogen gas, and then the temperature of the four-necked flask was raised to 80 ° C. in a nitrogen atmosphere while stirring. When the temperature reached 80 ° C., 0.1 part of a peroxide initiator (Nyper BMT-K40: manufactured by NOF Corporation) was added to initiate the reaction. After 10 minutes from the start of the reaction, a mixture of 60 parts of the remaining monomer mixture, 20 parts of ethyl acetate, and 0.1 part of a peroxide-based initiator (Niper BMT-K40: manufactured by NOF Corporation) The polymerization was continued under reflux while being uniformly added dropwise over 1 hour 30 minutes. 1 hour and 30 minutes after the completion of the dropwise addition of the monomer, 0.3 part of 1,1′-azobis-1-cyclohexanecarbonitrile and 40 parts of toluene were added as an initiator for post-addition, and another 1 hour and 30 minutes. By reacting, a solution of a methacrylic copolymer (1) having a solid content of 45.9% and a weight average molecular weight (Mw) of 68,000 was obtained.

  In a four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube and reflux condenser, and dropping funnel, 40 parts of a monomer mixture consisting of 94 parts of butyl acrylate and 6 parts of acrylic acid, and 60 parts of ethyl acetate were placed. After replacing the air in the four-necked flask with nitrogen gas, the temperature of the mixture in the four-necked flask was raised to 80 ° C. in a nitrogen atmosphere while stirring, and the peroxide system started when the temperature reached 80 ° C. 0.1 parts of an agent (Nyper BMT-K40: manufactured by NOF Corporation) was added to initiate the reaction. After 10 minutes from the start of the reaction, a mixture of 60 parts of the remaining monomer mixture, 20 parts of ethyl acetate, and 0.1 part of a peroxide-based initiator (Niper BMT-K40: manufactured by NOF Corporation) The polymerization was continued under reflux while being uniformly added dropwise over 1 hour 30 minutes. 1 hour and 30 minutes after the completion of the dropwise addition of the monomer, 0.3 part of 1,1′-azobis-1-cyclohexanecarbonitrile and 40 parts of toluene were added as an initiator for post-addition, and another 1 hour and 30 minutes. The reaction was performed to obtain a solution of an acrylic copolymer (1) having a solid content of 45.9% and a weight average molecular weight (Mw) of 760,000.

  For 100 parts of a mixed solution obtained by mixing 50 parts of the methacrylic copolymer (1) solution and 50 parts of the acrylic copolymer (1) solution, “Coronate L-55E” (modified TDI isocyanate, solid Min 55%, manufactured by Nippon Polyurethane Co., Ltd.) 1.5 parts, legal pigment (Yellow 201 No. 201) 2 parts were added and stirred sufficiently to obtain a solution (1) of (meth) acrylic adhesive.

(Production Example 8)
In a four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube and reflux condenser, and dropping funnel, 40 parts of a monomer mixture consisting of 94 parts of butyl acrylate and 6 parts of acrylic acid, and 60 parts of ethyl acetate were placed. After replacing the air in the four-necked flask with nitrogen gas, the temperature of the mixture in the four-necked flask was raised to 80 ° C. in a nitrogen atmosphere while stirring, and the peroxide system started when the temperature reached 80 ° C. 0.1 parts of an agent (Nyper BMT-K40: manufactured by NOF Corporation) was added to initiate the reaction. After 10 minutes from the start of the reaction, a mixture of 60 parts of the remaining monomer mixture, 20 parts of ethyl acetate, and 0.1 part of a peroxide-based initiator (Niper BMT-K40: manufactured by NOF Corporation) The polymerization was continued under reflux while being uniformly added dropwise over 1 hour 30 minutes. 1 hour and 30 minutes after the completion of the dropwise addition of the monomer, 0.3 part of 1,1′-azobis-1-cyclohexanecarbonitrile and 40 parts of toluene were added as an initiator for post-addition, and another 1 hour and 30 minutes. The reaction was performed to obtain a solution of an acrylic copolymer (1) having a solid content of 45.9% and a weight average molecular weight (Mw) of 760,000.

  For 100 parts of the acrylic copolymer (1) solution, 1.5 parts of “Coronate L-55E” (modified TDI isocyanate, solid content 55%, manufactured by Nippon Polyurethane Co., Ltd.), legal dye (blue No. 1) 2 parts were added and sufficiently stirred to obtain an acrylic pressure-sensitive adhesive solution (2).

(Production Example 9)
To a kneader equipped with a stirrer, ethylene / propylene / 5-ethylidene-2-norbornene terpolymer (ethylene unit amount 66 mass%, propylene unit amount 29.5 mass%, 5-ethylidene-2-norbornene unit amount) 4.5 parts by mass, intrinsic viscosity 4.7 dl / g) 35 parts, mineral oil (paraffinic mineral oil softener, paraffin chain carbon number in total carbon number 73%, naphthene ring carbon number in total carbon number 27% , Weight average molecular weight 1200) 35 parts, propylene / ethylene random copolymer (density 0.90 g / cm ³ , MFR (temperature 230 ° C., load 21 N) 23 g / 10 min) 27 parts, propylene / 1-butene crystalline copolymer (propylene unit content 71 mol%, melt viscosity 8,000 cps (190 ° C.), a density 0.87g / cm ^3, Mn6,500) ³ parts was added, 160 ° C. It was stirred for 3 hours. Furthermore, 0.4 part of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 0.5 part of N, N′-m-phenylenebismaleimide, low sulfur carbon black (sulfur amount 0. 2 wt%) 0.5 part, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate 0.3 part was added and stirred for 1 hour. A black thermoplastic elastomer composition was obtained.
The obtained black thermoplastic elastomer composition was heated and melted to 160 ° C., poured into a smooth bat that had been heated to 160 ° C. in advance to a weight of 500 g / m ² , and then cooled to produce a resin sheet. did. Furthermore, a releasable sheet was bonded to both surfaces of this resin sheet.

The abbreviations of the styrenic block copolymer (A) shown in Table 1 are shown below.
SEBS1: SEBS, styrene ratio 34% by weight, triblock content 100%
SEBS2: SEBS, styrene ratio 30% by weight, triblock content 30%, diblock content 70%
SEBS3: SEBS, styrene ratio 31% by weight, triblock content 100%
SEPS1: SEPS, styrene ratio 18% by weight, triblock content 100%
SEPS2: SEPS, styrene ratio 13% by weight, triblock content 100%
SEEPS1: SEEPS, styrene ratio 32% by weight, triblock content 100%
SEEPS 2: SEEPS, styrene ratio 30% by weight, triblock content 100%

The abbreviations of the mineral oil softener (B) listed in Table 1 are shown below.
Mineral oil 1: Paraffinic mineral oil softener, paraffin chain carbon number in total carbon number: 73%, naphthene ring carbon number in total carbon number: 27%, weight average molecular weight 1200
Mineral oil 2: Naphthenic mineral oil softener, paraffin chain carbon number in total carbon number: 40.7%, naphthene ring carbon number in total carbon number: 47.2%, aromatic ring carbon in total carbon number Number: 12.1%, weight average molecular weight 1800
Mineral oil 3: Paraffinic mineral oil softener, paraffin chain carbon number in total carbon number: 71%, naphthenic ring carbon number in total carbon number: 29%, weight average molecular weight 1000

Abbreviations for tackifying resins (C) listed in Table 1 are shown below.
Tackifying resin 1: Hydrogenated petroleum-based tackifying resin, softening point 100 ° C.
Tackifying resin 2: Hydrogenated terpene tackifying resin, softening point 115 ° C.
Tackifying resin 3: Hydrogenated petroleum-based tackifying resin, softening point 125 ° C
Tackifying resin 4: hydrogenated terpene tackifying resin, softening point 100 ° C.

Abbreviations for the colorant (D) listed in Table 1 are shown below.
Iron titanate: Inorganic red pigment Ultraviolet: Inorganic blue pigment Yellow iron oxide: Inorganic yellow pigment Cobalt titanate: Inorganic green pigment Black iron oxide: Inorganic black pigment

Abbreviations of other components listed in Table 1 are shown below.
Antioxidant: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
Fragrance: Methyl benzoate (ester flavor)

[Example 1]
A release sheet on one side is peeled from the resin sheet obtained in Production Example 1 above, a PET sheet is bonded, and a laminate (1) having a configuration of “PET sheet / resin composition layer / release sheet” is prepared. Obtained.

[Example 2]
A release sheet on one side is peeled from the resin sheet obtained in Production Example 3 above, a PET sheet is bonded, and a laminate (2) having a configuration of “PET sheet / resin composition layer / release sheet” is obtained. Obtained.

[Example 3]
The resin composition obtained in Production Example 2 was charged into a handy type hot melt dispenser, melted, and directly discharged onto the adherend from the hot melt dispenser to form an image. An oil painting-like image formation (1) having a three-dimensional effect was obtained.

[Example 4]
The releasable sheet was peeled off from the resin sheets obtained in Production Examples 2 and 3, respectively, cut to give a unique color, mixed by heating, melting and mixing. After cooling to room temperature, these are cut and arranged like a patchwork, the release sheet is peeled off from the black resin sheet obtained in Production Example 5, cut thinly, placed at the boundary, and re-launched as a whole. An integrated stained glass-like image formed product (2) was obtained by heating and melting.

[Example 5]
The releasable sheet was peeled off from the resin sheets obtained in Production Examples 1, 2, and 3, respectively, cut and arranged like a torn picture. Thereafter, it was heated and melted to be integrated to obtain a landscape-like image formation like an oil painting. The releasable sheet was peeled off from the transparent resin sheet obtained in Production Example 6, and the landscape-like image-formed product was arranged on the surface and heated and melted to obtain an integrated image-formed product (3). .

[Example 6]
The release sheet was peeled off from the resin sheets obtained in Production Examples 1 and 2, respectively, and heated and melted to produce a thicker image formed product, which was cooled in a stone-like shape. Similarly, the releasable sheet was peeled off from the resin sheets obtained in Production Examples 3 and 4, respectively, and a similar thick image formed product was produced and cooled. The respective image formed products were cut, arranged like a patchwork, and further heated and melted to obtain a three-dimensional image formed product (4).

[Example 7]
A release sheet is peeled from the resin sheet obtained in Production Example 1, and sequins, fluorescent materials, phosphorescent materials, inorganic powders, plastic beads, glass beads, plated plastic beads, and a design cloth are formed thereon. Then, only the surface of the resin composition was melted and adhered by heating to obtain an image-formed product (5) having a three-dimensional design.

[Comparative Example 1]
The (meth) acrylic pressure-sensitive adhesive solution (1) obtained in Production Example 7 was poured into a smooth bat so that the thickness after drying was 0.5 mm, and the solvent was removed by heating. An adhesive layer was formed, and a PET sheet and a release sheet were further bonded to obtain a laminate (3) having a configuration of “PET sheet / (meth) acrylic adhesive layer / release sheet”.

[Comparative Example 2]
The acrylic adhesive solution (2) obtained in Production Example 8 was poured into a smooth bat so that the thickness after drying was 0.5 mm, and the solvent was removed by heating to form an acrylic adhesive layer. Furthermore, a PET sheet and a releasable sheet were bonded together to obtain a laminate (4) having a configuration of “PET sheet / acrylic pressure-sensitive adhesive layer / releasable sheet”.

[Comparative Example 3]
A release sheet on one side is peeled from the resin sheet obtained in Production Example 9 above, a PET sheet is bonded, and a laminate (5) having a configuration of “PET sheet / resin composition layer / release sheet” is obtained. Obtained.

[Re-peeling test]
The laminate and the image-formed product were adjusted so that the contact surface to the adherend was 50 mm long × 50 mm wide to obtain a test piece. The releasable sheet was peeled off as necessary, and the test piece was attached to a window glass, wallpaper, or acrylic plate as an adherend in an atmosphere at 25 ° C. After standing still in a 50 ° C. atmosphere for 7 days, the resin composition was peeled off and the resin composition remaining on the surface of the window glass, wallpaper, and acrylic plate, and bleeding were visually confirmed. The results are shown in Table 2.
[Criteria]
○: The resin composition remained and did not exude on the adherend.
X: Residue of the resin composition remained on the adherend and exuded.

[Peeling off test]
The laminate and the image-formed product were adjusted so that the contact surface to the adherend was 50 mm long × 50 mm wide to obtain a test piece. The releasable sheet was peeled off as needed, and the test piece was stuck on a window glass, wallpaper, and an acrylic board at 25 degreeC atmosphere. Immediately after application, the film was peeled off at high speed, and the peel force was evaluated by sensory evaluation. The results are shown in Table 2.
[Criteria]
(Double-circle): It was able to peel easily.
○: Tack was strong but could be peeled without breaking.
X: It is broken and difficult to peel.

[Presence or absence of colorant transfer]
The laminate and the image-formed product were adjusted so that the contact surface to the adherend was 50 mm long × 50 mm wide to obtain a test piece. If necessary, the release sheet is peeled off, the test piece is affixed to glass, wallpaper, and acrylic plate in an atmosphere at 25 ° C, and is allowed to stand for 7 days in an atmosphere at 50 ° C. After leaving still for 1 hour, it peeled from glass, a wallpaper, and an acrylic board, the adherend surface was confirmed visually, and it evaluated as follows. The results are shown in Table 2.
[Criteria]
○: No migration of the colorant was observed on the adherend.
(Triangle | delta): Although transfer of the coloring agent was confirmed to the to-be-adhered body, it was able to remove easily.
X: The colorant migrates to the adherend and cannot be easily removed.

[Heat resistance test]
The laminate and the image-formed product were adjusted so that the contact surface to the adherend was 50 mm long × 50 mm wide to obtain a test piece. If necessary, the release sheet is peeled off, left in an atmosphere of 80 ° C. for 500 hours, and left in an atmosphere of 23 ° C. and a relative humidity of 65% for 1 hour. It was evaluated as follows. The results are shown in Table 2.
[Criteria]
A: No change in shape was confirmed.
○: Some deformation was confirmed, but the overall shape was almost unchanged.
X: The entire shape was deformed.

  Various touch images (stained glass tone, oil painting tone, stone tone, etc.) can be obtained by the resin composition of the present invention, and hands are not stained at the time of production. When adhering, it can be easily washed with water or soapy water. In addition, it has a feature that various image formation is possible with personal sense, and is promising as a material for indoor space design.

Claims (6)

A resin composition comprising a styrenic block copolymer (A), a mineral oil softener (B), a tackifier resin (C) and a colorant (D),
The styrene block copolymer (A) has a styrene ratio of 10 to 40% by weight, and has a triblock structure.
The mineral oil softener (B) has a weight average molecular weight of 700 to 10,000.
The tackifying resin (C) has a softening point of 80 to 160 ° C.,
Styrenic block copolymer (A) 3 to 65 parts by weight, mineral oil softener (B) 10 to 95.9 parts by weight, tackifier resin (C) 1 to 50 parts by weight and colorant (D) 0.1 A resin composition obtained by blending 10 parts by weight to 10 parts by weight with a total of 100 parts by weight.   The resin composition according to claim 1, wherein the resin composition has a viscosity at 170 ° C. of 500 to 50,000 mPa · s.   The laminated body formed by laminating | stacking the resin composition layer formed from the resin composition of Claim 1 or 2 on the single side | surface or both surfaces of a sheet-like base material. The laminate according to claim 3, wherein the coating amount of the resin composition layer is 1-1000 g / m ² .   An image formed product obtained by processing the resin composition according to claim 1.   An image formed product obtained by processing the laminate according to claim 3.