JP2017078119A - Adhesive sheet and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive sheet which hardly causes delamination and is excellent in dimensional stability.SOLUTION: In the adhesive sheet, a polyvinyl chloride substrate layer, a first primer layer, a second primer layer, and a hot-melt adhesive layer are laminated in this order. The first primer layer contains an ethylene-vinyl acetate copolymer. The second primer layer contains a mixture of a urethane resin and an ethylene-vinyl acetate copolymer. The hot-melt adhesive layer contains a polyolefin resin.SELECTED DRAWING: Figure 1

Description

The present invention relates to an adhesive sheet and a molded article.

The adhesive sheet is used, for example, for protecting the surface of the adherend, decorating, and the like, and the configuration of the adhesive sheet includes, for example, a configuration in which a resin base material layer and an adhesive layer are laminated. When the composition of the resin used for the resin substrate layer and the adhesive layer is different, the adhesion between the resin substrate layer and the adhesive layer may be insufficient. Therefore, it has been studied to provide a primer layer between the resin base material layer and the adhesive layer to improve the adhesion between the resin base material layer and the adhesive layer (for example, Patent Document 1 and Patent Document 2). etc).

Patent Document 1 discloses a laminate in which a layer having a specific polyolefin adhesive resin (A) and a layer having a specific polar adhesive resin (B) are continuous. According to the above laminate, it has excellent adhesion to polyolefin resin substrates, and also has good adhesion to highly polar substrates such as polyester resins, and has low tack and handleability. It is disclosed that a primer, a hot melt adhesive film, and a decorative film can be provided. Patent Document 2 discloses a decorative material in which a decorative layer is formed on a primer composition containing a urethane prepolymer via an adhesive. According to the above-mentioned decorative material, the adhesiveness with the decorative layer is good, the base material can be reinforced without lowering the workability, the overcoating is not required, and the drying time can be shortened by reducing the coating amount. It is disclosed.

JP 2014-008694 A Japanese Patent No. 5078959

A vinyl chloride resin is suitable for use as a base material of an adhesive sheet because it has good elongation and is not easily broken. For the adhesive layer, since it is excellent in workability, it has been studied to use a hot-melt adhesive that exhibits an adhesive force in a high temperature environment. Especially, since the adhesiveness to the to-be-adhered body containing polyolefin resin is favorable, the hot melt adhesive containing polyolefin resin is used suitably. However, the resin layers containing resins having different compositions such as polyvinyl chloride and polyolefin resin have insufficient adhesion, so that delamination may occur, and sufficient adhesive strength and In order to obtain dimensional stability, there was room for examination.

From the above, there has been a demand for an adhesive sheet having excellent dimensional stability in which delamination does not easily occur between a base material layer and an adhesive layer having different compositions.

The inventor has a first primer layer containing an ethylene vinyl acetate copolymer, a urethane resin and an ethylene acetate between a polyvinyl chloride base material layer and a hot melt adhesive layer containing a polyolefin resin. By providing a second primer layer containing a mixture with a vinyl copolymer, the adhesion between the polyvinyl chloride base material layer and the hot melt adhesive layer is improved, delamination hardly occurs, and dimensional stability is improved. The inventors have found that an excellent adhesive sheet can be obtained and completed the present invention.

The adhesive sheet of the present invention is laminated in the order of a polyvinyl chloride substrate layer, a first primer layer, a second primer layer, and a hot melt adhesive layer, and the first primer layer is made of ethylene vinyl acetate. The second primer layer contains a mixture of a urethane resin and an ethylene vinyl acetate copolymer, and the hot melt adhesive layer contains a polyolefin resin. To do.

In the mixture of the urethane resin and the ethylene vinyl acetate copolymer, the ratio of the blending amount (parts by weight) of the urethane resin and the blending amount (parts by weight) of the ethylene vinyl acetate copolymer is 30:70. It is preferably ~ 70: 30.

The adhesive sheet is preferably a decorative adhesive sheet.

The molded article of the present invention is characterized in that the adhesive sheet of the present invention and an adherend containing a polycarbonate resin, acrylonitrile / butadiene / styrene resin, or polyolefin resin are laminated.

The adhesive sheet of the present invention includes a first primer layer containing an ethylene vinyl acetate copolymer and a urethane resin between a polyvinyl chloride base material layer and a hot melt adhesive layer containing a polyolefin resin. By disposing a second primer layer containing a mixture of ethylene and vinyl acetate copolymer, the adhesion between the polyvinyl chloride base material layer and the hot melt adhesive layer can be increased, Delamination hardly occurs and dimensional stability is excellent.

It is sectional drawing which showed an example of the adhesive sheet of this invention typically.

The adhesive sheet of the present invention is laminated in the order of a polyvinyl chloride substrate layer, a first primer layer, a second primer layer, and a hot melt adhesive layer, and the first primer layer is made of ethylene vinyl acetate. The second primer layer contains a mixture of a urethane resin and an ethylene vinyl acetate copolymer, and the hot melt adhesive layer contains a polyolefin resin. To do.

Hereinafter, the adhesive sheet of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view schematically showing an example of the adhesive sheet of the present invention. As shown in FIG. 1, the adhesive sheet 10 is laminated in the order of a polyvinyl chloride base layer 11, a first primer layer 12, a second primer layer 13, and a hot melt adhesive layer 14.

[Polyvinyl chloride substrate layer]
The polyvinyl chloride base material layer 11 is a base material layer made of a vinyl chloride resin composition. A polyvinyl chloride base material is suitably used as a base material for an adhesive sheet because it has good elongation and is difficult to break. In addition, the polyvinyl chloride base material is suitably used as the base material of the adhesive sheet because it has a high degree of design freedom, can be embossed, and has excellent printability, chemical resistance, and weather resistance.

The vinyl chloride resin composition is not particularly limited, and examples thereof include a composition containing a vinyl chloride resin and a plasticizer.

Examples of the vinyl chloride resin include vinyl chloride homopolymers, copolymers of vinyl chloride with other monomers copolymerizable with vinyl chloride, and the like. The vinyl chloride resin is preferably a vinyl chloride homopolymer from the viewpoint of excellent printability, visibility and dimensional stability.

Examples of other monomers copolymerizable with vinyl chloride include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene and styrene; methyl acrylate, ethyl acrylate, methyl methacrylate, and the like. (Meth) acrylic acid esters; maleic acid diesters such as dibutyl maleate and diethyl maleate; fumaric acid diesters such as dibutyl fumarate and diethyl fumarate; vinyl cyanide such as acrylonitrile and methacrylonitrile; vinylidene chloride and bromide And vinyl halides such as vinyl; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether. The content of the other polymerizable monomer in the vinyl chloride resin is usually 50% by weight or less, preferably 10% by weight or less.

The average degree of polymerization of the vinyl chloride resin is not particularly limited, but a preferred lower limit is 700 and a preferred upper limit is 1400. When the average degree of polymerization is less than 700, when the resin composition is melted and calendered, the surface of the molded product may become rough or the molded product may become brittle. When the average degree of polymerization exceeds 1400, the melted resin composition may have insufficient heat resistance and cannot be processed, or the heat resistance and weather resistance of the molded product may be deteriorated. The average degree of polymerization of the vinyl chloride resin can be measured in accordance with JISK-6721 “Testing method of vinyl chloride resin”.

The plasticizer is not particularly limited, and those usually used in the field of sheets can be used. For example, octyl phthalate (di-2-ethylhexyl phthalate (DOP)), dibutyl phthalate, dinonyl phthalate, etc. Phthalic acid diesters; aliphatic dibasic acid diesters such as dioctyl adipate and dioctyl sebacate; phosphoric acid triesters such as tricresyl phosphate and trioctyl phosphate; epoxy plasticizers such as epoxidized soybean oil and epoxy resin; High molecular polyester plasticizer and the like. These may be used alone or in combination of two or more.

Examples of the polymer polyester plasticizer include polyalkylene glycol diesters such as polyethylene glycol diester, polypropylene glycol diester, and polyethylene glycol polypropylene glycol diester of phthalic acid; polyethylene glycol diesters of aliphatic dibasic acids such as adipic acid and sebacic acid. Polyalkylene glycol diesters such as polypropylene glycol diester and polyethylene glycol polypropylene glycol diester;

The minimum with preferable content of the said plasticizer with respect to 100 mass parts of said vinyl chloride-type resin is 5 weight part, and a preferable upper limit is 40 weight part. When the content of the plasticizer is less than 5 parts by weight, the flexibility is poor and the surface shape of the adherend may not be followed when attached to the adherend. When the content of the plasticizer exceeds 40 parts by weight, the plasticizer bleeds on the surface of the polyvinyl chloride base layer 11 to deteriorate the sharpness of the surface of the polyvinyl chloride base layer 11 or the like. May bleed to the primer layer 12 side and reduce the adhesive strength with the first primer layer 12. The minimum with more preferable content of the said plasticizer with respect to 100 mass parts of said vinyl chloride-type resin is 15 weight part, and a more preferable upper limit is 30 weight part.

An appropriate amount of various additives may be added to the vinyl chloride resin composition as necessary. Examples of the additive include a lubricant, an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a colorant, a modifier, a flame retardant, an antistatic agent, a reinforcing agent, an antifogging agent, a filler, Examples include diluents and fungicides. Examples of the heat stabilizer include metal organic acid compounds containing lead (Pb), barium (Ba), zinc (Zn), calcium (Ca), tin (Sn), and the like.

The preferable lower limit of the thickness of the polyvinyl chloride base material layer 11 is 50 μm, the preferable upper limit is 400 μm, the more preferable lower limit is 80 μm, the more preferable upper limit is 300 μm, the still more preferable lower limit is 100 μm, and further preferable. The upper limit is 200 μm. When the thickness of the polyvinyl chloride base material layer is less than 50 μm, it may become too thin when being attached to an adherend, and the base may be transparent. When the thickness of the polyvinyl chloride base material layer exceeds 400 μm, the followability of the adhesive sheet may be insufficient when affixed to the adherend.

[First primer layer]
The first primer layer 12 contains an ethylene vinyl acetate copolymer. Since the ethylene vinyl acetate copolymer has a polar group, it is highly polar and has good affinity with a vinyl chloride resin having a high polarity. Therefore, the adhesiveness of the polyvinyl chloride base material layer 11 and the 2nd primer layer 13 can be made favorable because the 1st primer layer 12 contains an ethylene vinyl acetate copolymer.

If the said ethylene vinyl acetate copolymer is a copolymer of ethylene and vinyl acetate, it will not specifically limit, Arbitrary ethylene vinyl acetate copolymers can be employ | adopted in the range which does not impair the effect of this invention. As said ethylene vinyl acetate copolymer, the copolymer of ethylene and vinyl acetate is mentioned, for example, KV-128 (made by Konishi Co., Ltd.) etc. can be used. As said ethylene vinyl acetate copolymer, another compound may be copolymerized besides ethylene and vinyl acetate, for example, a glycidyl methacrylate-ethylene-vinyl acetate copolymer etc. are mentioned.

About content of the said ethylene vinyl acetate copolymer in the 1st primer layer 12, with respect to 100 weight part of resin compositions which comprise the 1st primer layer 12, content of the said ethylene vinyl acetate copolymer is preferable. The lower limit is 70 parts by weight, the preferred upper limit is 100 parts by weight, the more preferred lower limit is 80 parts by weight, and the more preferred upper limit is 90 parts by weight.

The 1st primer layer 12 may contain urethane type resin other than the said ethylene vinyl acetate copolymer, for example, and does not need to contain it. In order to increase the adhesive force to the polyvinyl chloride base material layer 11, it is preferable that the first primer layer 12 is composed only of the ethylene vinyl acetate copolymer. When the first primer layer 12 contains the urethane resin, it is preferable that the ethylene vinyl acetate copolymer and the urethane resin are not crosslinked. Adhesion with the polyvinyl chloride base material layer 11 can be improved by coating the polyvinyl chloride base material layer 11 without crosslinking the ethylene vinyl acetate copolymer and the urethane resin. This is because it can.

The urethane resin is obtained, for example, by reacting a polyol and an isocyanate. As said urethane type resin, T-5265 (made by Hirono Chemical Co., Ltd.), P-OL (made by No Tape Industrial Co., Ltd.), etc. can be used, for example.

It does not specifically limit as said polyol, For example, polyether polyol, polycaprolactone polyol, polycarbonate polyol, polyester polyol etc. are mentioned.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polypropylene triol, polypropylene tetraol, polytetramethylene glycol, polytetramethylene triol, polyalkylene glycols such as copolymers thereof, and side chains introduced into these. And derivatives having a branched structure introduced therein, modified products, and mixtures thereof.

Examples of the polycaprolactone polyol include polycaprotectone glycol, polycaprolactone triol, polycaprolactone tetraol, derivatives in which side chains are introduced or branched structures are introduced, modified products, and mixtures thereof. Can be mentioned.

As said polycarbonate polyol, the reaction material of a dialkyl carbonate and diol is mentioned, for example.

Examples of the dialkyl carbonate include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; diaryl carbonates such as diphenyl carbonate; and alkylene carbonates such as ethylene carbonate. These may be used alone or in combination of two or more.

Examples of the diol include 1,4-butanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and 2-methyl-1,8. -Octanediol, 1,9-nonanediol, 1,10-dodecanediol, 2-ethyl-1,6-hexanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5- Examples include pentanediol, neopentyl glycol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2′-bis (4-hydroxycyclohexyl) -propane, and the like. These may be used alone or in combination of two or more. As said diol, C4-C9 alicyclic or alicyclic diol is preferable, for example, 1, 4- butane diol, diethylene glycol, 1, 5- pentane diol, 1, 6-hexane diol, 3- Methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1 , 8-octanediol and 1,9-nonanediol are preferably used alone or in combination of two or more. Examples of the diol include a copolycarbonate diol composed of 1,6-hexanediol and 3-methyl-1,5-pentanediol, and a copolycarbonate diol composed of 1,6-hexanediol and 1,5-pentanediol. Is also preferable.

Further, as the polycarbonate polyol, for example, polycarbonate glycol, polycarbonate triol, polycarbonate tetraol, derivatives in which side chains are introduced or branched structures are introduced therein, modified products, and mixtures thereof may be used. it can.

As said polyester polyol, what dehydrated and condensed dicarboxylic acid and the glycol component is mentioned, for example.

Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid; oxalic acid; malonic acid; succinic acid; glutaric acid; adipic acid; azelaic acid; Can be mentioned.

Examples of the glycol component include ethylene glycol, 1,4-butanediol, diethylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,5-pentanediol, 1,9-nonanediol, Aliphatic glycols such as ethylene glycol; alicyclic glycols such as 1,4-cyclohexanedimethanol; aromatic diols such as p-xylene diol; polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. Can be mentioned.

Examples of the isocyanate include tetramethylene diisocyanate, dodecamethylene diisocyanate, 1,4-butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. Diisocyanates such as 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate; isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate , Cyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane Tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1 , 5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate and other aromatic diisocyanates; dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α, α, α, α-tetramethylxyl Examples include aromatic aliphatic diisocyanates such as range isocyanate. Of these, diphenylmethane diisocyanate is preferably used from the viewpoint of cost and safety. These may be used alone or in combination of two or more.

The urethane resin may be urethane acrylate. As for the said urethane acrylate, what introduce | transduced the (meth) acrylic-acid monomer to the urethane type resin obtained by making the said polyol and isocyanate react, for example is mentioned.

When the first primer layer 12 contains the urethane resin, the amount of the urethane resin in the first primer layer 12 (parts by weight) and the amount of the ethylene vinyl acetate copolymer (parts by weight). And the ratio is preferably 1:99 to 25:75. When the ratio of the urethane resin is high, the adhesion between the first primer layer 12 and the polyvinyl chloride base material layer 11 may be insufficient. The ratio of the blending amount (parts by weight) of the urethane resin and the blending amount (parts by weight) of the ethylene vinyl acetate copolymer is more preferably 1:99 to 20:80, and 1:99 to 15 : 85 is more preferable.

When the first primer layer 12 contains the urethane resin, the first primer layer 12 may further contain a curing agent.

The curing agent is not particularly limited. For example, isocyanate curing agents such as tolylene diisocyanate and hexamethylene diisocyanate; epoxy curing agents such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and tetraglycidyl xylenediamine; Metal chelating agents such as Al, Ni and Zn; amino resin-based curing agents such as melamine compounds. As the isocyanate curing agent, for example, Desmodur L-75 (manufactured by Sumika Bayer Urethane Co., Ltd.), P-OL (manufactured by No Tape Industrial Co., Ltd.) or the like can be used.

The first primer layer 12 is a colorant, a light stabilizer, a heat stabilizer, an antioxidant, an antifungal agent, a flame retardant, a stabilizer, if necessary, within a range not impairing the effects of the present invention. Various additives such as ultraviolet absorbers, pigments, modifiers, fillers, antistatic agents and antifungal agents may be contained.

A preferable lower limit of the thickness of the first primer layer 12 is 0.2 μm, a preferable upper limit is 5 μm, a more preferable lower limit is 0.5 μm, and a more preferable upper limit is 2 μm.

[Second primer layer]
The second primer layer 13 contains a mixture of a urethane resin and an ethylene vinyl acetate copolymer. The second primer layer 13 contains a mixture of a urethane-based resin and an ethylene vinyl acetate copolymer, so that the polarity is adjusted step by step, and the first primer layer 12 and the hot melt adhesive layer 14 Adhesiveness can be made favorable. In particular, urethane resins are close in polarity to polyolefin resins and have high affinity with polyolefin resins. Therefore, the adhesiveness with the hot-melt-adhesive agent layer 14 containing polyolefin resin with low polarity can be improved because the 2nd primer layer 13 contains urethane type resin.

As said urethane type resin, the thing similar to what was mentioned by said 1st primer layer 12 can be used. The type of urethane resin contained in the first primer layer 12 was the same as the type of urethane resin used in the mixture of the urethane resin and ethylene vinyl acetate copolymer of the second primer layer 13. It may be different or different.

As said ethylene vinyl acetate copolymer, the thing similar to the thing quoted by said 1st primer layer 12 can be used. Types of ethylene vinyl acetate copolymer contained in first primer layer 12 and types of ethylene vinyl acetate copolymer used in a mixture of urethane-based resin and ethylene vinyl acetate copolymer of second primer layer 13 And may be the same or different.

The second primer layer 13 may further contain a curing agent. As the curing agent, the same ones as those mentioned in the first primer layer 12 can be used. The content of the curing agent may be 1 part by weight or more and 15 parts by weight or less with respect to a total of 100 parts by weight of the urethane resin and the ethylene vinyl acetate copolymer.

In the mixture of the urethane resin and the ethylene vinyl acetate copolymer, the ratio of the blending amount (parts by weight) of the urethane resin and the blending amount (parts by weight) of the ethylene vinyl acetate copolymer is 30:70. It is preferably ~ 70: 30. When the ratio of the urethane resin is low, the adhesion between the second primer layer 13 and the hot melt adhesive layer 14 may be insufficient. When the ratio of the urethane resin is high, the second primer Adhesion between the layer 13 and the first primer layer 12 may be insufficient. The blending ratio of the urethane resin and the ethylene vinyl acetate copolymer is more preferably 35:65 to 65:35, and still more preferably 40:60 to 60:40.

The second primer layer 13 is a colorant, a light stabilizer, a heat stabilizer, an antioxidant, an antifungal agent, a flame retardant, a stabilizer, as necessary, as long as the effects of the present invention are not impaired. Various additives such as ultraviolet absorbers, pigments, modifiers, fillers, antistatic agents and antifungal agents may be contained.

The preferable lower limit of the thickness of the second primer layer 13 is 0.2 μm, the preferable upper limit is 5 μm, the more preferable lower limit is 0.5 μm, and the more preferable upper limit is 2 μm.

[Hot melt adhesive layer]
The hot melt adhesive layer 14 contains a polyolefin resin. Since the hot melt adhesive layer 14 contains a polyolefin resin, the polarity is close to that of a polycarbonate resin, ABS resin, polyolefin resin, etc., so that the adherend is a polycarbonate resin, ABS resin, polyolefin resin. Sufficient adhesiveness can be expressed even on an adherend containing a resin or the like. Among these, it can be suitably used for adherends containing polyolefin resins such as polyethylene resins and polypropylene resins, and particularly preferably used for adherends containing polypropylene resins. it can. Moreover, it can use suitably for the construction in a high temperature environment.

The hot-melt adhesive layer 14 has a low polarity because it contains a polyolefin resin, and has low adhesion to the polyvinyl chloride base material layer. Therefore, a first primer layer 12 containing an ethylene vinyl acetate copolymer, a urethane resin and an ethylene vinyl acetate copolymer are interposed between the polyvinyl chloride base material layer 11 and the hot melt adhesive layer 14. By arranging the second primer layer 13 to be contained, the polarity is adjusted stepwise, and the adhesion between the polyvinyl chloride base material layer 11 having a different composition and the hot-melt adhesive layer 14 containing the polyolefin resin. Can be improved. Therefore, if the order of lamination of the first primer layer 12 and the second primer layer 13 is reversed, the adhesion between the polyvinyl chloride base material layer 11 and the hot melt adhesive layer 14 becomes insufficient, and the polychlorination Delamination easily occurs between the vinyl base layer 11 and the hot melt adhesive layer 14.

Examples of the polyolefin resin include polyethylene, polypropylene, poly-1-butene, polyisobutylene, polymethylpentene, propylene-ethylene copolymer, ethylene-propylene-diene copolymer, and ethylene / butene-1 copolymer. Polyolefins such as ethylene / octene copolymers; cyclic polyolefins such as copolymers of cyclopentadiene and ethylene and / or propylene; ethylene / vinyl acetate copolymers (EVA), ethylene / ethyl acrylate copolymers (EEA) ), Polyolefins into which polar groups such as isobutylene / maleic anhydride copolymer have been introduced; acid-modified polypropylenes such as maleic anhydride-modified polypropylene, maleic acid-modified polypropylene, and acrylic acid-modified polypropylene. These may be used alone or in combination of two or more. As the hot melt adhesive layer 14, for example, AT004 (manufactured by Kaneka Corporation), PPET1303S, PPET1025 (manufactured by Toagosei Co., Ltd.) or the like can be used.

The hot melt adhesive layer 14 may have a softening temperature of 100 ° C to 160 ° C. If the softening temperature of the hot melt adhesive layer 14 is less than 100 ° C., peeling or sticking may occur during use, and if it exceeds 160 ° C., the temperature at the time of application increases, and the adhesive sheet 10 itself or the adherend This is because there is a risk of heat degradation.

Regarding the content of the polyolefin resin in the hot melt adhesive layer 14, the preferred lower limit of the content of the polyolefin resin with respect to 100 parts by weight of the resin composition constituting the hot melt adhesive layer 14 is 70 parts by weight. The preferred upper limit is 100 parts by weight, the more preferred lower limit is 80 parts by weight, and the more preferred upper limit is 90 parts by weight.

The hot melt adhesive layer 14 may further include a colorant, a light stabilizer, a heat stabilizer, an antioxidant, an antifungal agent, a flame retardant, a stabilizer, as long as the effects of the present invention are not impaired. Various additives such as ultraviolet absorbers, pigments, modifiers, fillers, antistatic agents and antifungal agents may be contained.

The preferable lower limit of the thickness of the hot melt adhesive layer 14 is 10 μm, the preferable upper limit is 100 μm, the more preferable lower limit is 20 μm, and the more preferable upper limit is 80 μm. When the thickness of the hot melt adhesive layer 14 is less than 10 μm, it may not be possible to ensure sufficient adhesion to the adherend. When the thickness of the hot-melt adhesive layer 14 exceeds 100 μm, there is a concern that the trace of the adhesive layer may be lifted on the surface of the adhesive sheet 10 when the hot-melt adhesive layer 14 is stretched and used at a high temperature.

The surface of the hot melt adhesive layer 14 on the second primer layer 13 side may be subjected to corona treatment. The adhesive sheet 10 has sufficient adhesion between the hot melt adhesive layer 14 and the second primer layer 13, but after the corona treatment on the surface of the hot melt adhesive layer 14, the second primer By laminating the layer 13, the adhesion between the hot melt adhesive layer 14 and the second primer layer 13 can be further enhanced. The corona treatment can be performed, for example, by irradiating the surface of the hot melt adhesive layer 14 with corona discharge. By the corona treatment, the polar group can be exposed and modified on the surface of the hot melt adhesive layer 14.

The adhesive sheet 10 may further have a release layer on the hot melt adhesive layer 14 side. As the release layer, those usually used in the field of sheets can be used. Examples of the release layer include those obtained by coating the surface of a polyethylene terephthalate (PET) film, fine paper or the like with a silicone release agent, an alkyd release agent, a fluorine release agent, or the like. The release layer may be subjected to a surface treatment only on the surface on the hot melt adhesive layer 14 side.

The adhesive sheet 10 may be printed on the surface of the polyvinyl chloride base material layer 11 opposite to the first primer layer 12 or may be opposite to the first primer layer 12 of the polyvinyl chloride base material layer 11. You may have a printing layer in the side. Printing on the polyvinyl chloride substrate layer 11 or formation of the printing layer can be performed by, for example, offset printing, gravure printing, inkjet printing, screen printing, rotary screen printing, flexographic printing, electrostatic printing, or the like. Moreover, the polyvinyl chloride base material layer 11 may have fine irregularities on the surface opposite to the first primer layer 12 by embossing or the like.

The adhesive sheet 10 may further have a protective layer on the polyvinyl chloride base material layer 11 side. As the protective layer, those usually used in the field of sheets can be used. Examples of the protective layer include a resin layer made of polycarbonate resin, polypropylene resin, or the like.

Although the manufacturing method of the adhesive sheet 10 is not particularly limited, for example, the polyvinyl chloride base material layer 11 is formed by calendering or the like after melt-kneading the vinyl chloride resin composition using a Banbury mixer or the like. be able to. The first primer layer 12 can be formed, for example, by mixing an ethylene vinyl acetate copolymer with a diluting solvent, coating the polyvinyl chloride base layer 11 with a gravure roll, and drying the mixture. it can. The second primer layer 13 is prepared by, for example, mixing a urethane resin, an ethylene vinyl acetate copolymer, and a curing agent to obtain a mixture of the urethane resin and the ethylene vinyl acetate copolymer, and then using a gravure roll or the like. It can be formed by coating on the first primer layer 12 and drying. The hot melt adhesive layer 14 is made of, for example, an adhesive composition containing a polyolefin resin on the release layer using a general-purpose film forming apparatus such as various coating apparatuses, bar coats, doctor blades, or the like. It can be formed by coating and then drying. The adhesive sheet 10 can be obtained by laminating the hot melt adhesive layer 14 on the second primer layer 13. As the hot melt adhesive layer 14, a commercially available polyolefin-based hot melt adhesive sheet may be bonded onto the second primer layer 13.

The adhesive sheet 10 preferably has an adhesive strength measured by a 180 ° peel test of 30 N / 25 mm or more and 100 N / 25 mm or less at room temperature and normal humidity. The 180 ° peel test is performed by a method based on JIS Z 0237. By measuring the adhesive force, the adhesive force of the adhesive sheet 10 to the adherend can be confirmed. When the adhesive strength is less than 30 N / 25 mm, the adhesive strength to the adherend is insufficient, and the adhesive sheet 10 may float from the adherend during use. When the adhesive strength exceeds 100 N / 25 mm, it may be difficult to re-attach after being laminated on the adherend. The details of the 180 ° peel test method will be described later.

The adhesive sheet 10 can be used, for example, for protecting the surface of the adherend, decorating, and the like. Especially, it is preferable that the adhesive sheet 10 is a decorative adhesive sheet. When the adhesive sheet 10 is a decorative adhesive sheet, as described above, the surface of the polyvinyl chloride base material layer 11 opposite to the first primer layer 12 is printed, or the polyvinyl chloride base material It is preferable to have a printing layer on the opposite side of the layer 11 from the first primer layer 12.

The adherend is not particularly limited. For example, bicycles, motorcycles, automobiles, buses, trains and other vehicles; furniture, household appliances such as home appliances; cabinets, office desks, personal computers and other office supplies; Buildings, etc .; or these exterior parts or interior parts. Especially, it can use suitably for the interior component of a motor vehicle, or the interior component of a house.

The adhesive sheet 10 can be laminated on the adherend to produce a molded product. When the adhesive sheet 10 is a decorative adhesive sheet, it can be applied to the surface of the adherend to enhance the design.

Examples of the material of the adherend include, for example, polyolefin resins such as polyethylene resins, polypropylene resins, and olefin thermoplastic elastomers; polystyrene resins, polyethylene terephthalate resins, polyvinyl alcohol resins, vinyl chloride resins, Examples thereof include polyamide resins, polyacetal resins, polycarbonate resins, acrylonitrile / butadiene / styrene (ABS) resins, ionomer resins, and resin compositions obtained by adding various additives such as inorganic fibers to these resins. Especially, high adhesive force can be expressed with respect to polyolefin resin, such as polyethylene resin, polypropylene resin, and olefin thermoplastic elastomer.

In particular, the adhesive sheet 10 exhibits a high adhesive force with respect to a polycarbonate resin, an acrylonitrile / butadiene / styrene (ABS) resin, and a polyolefin resin. That is, the molded product of the present invention is a laminate of the adhesive sheet 10 and an adherend containing a polycarbonate resin, ABS resin, or polyolefin resin. Furthermore, in order to express higher adhesive force with respect to the polypropylene resin, the molded article of the present invention is preferably a laminate of the adhesive sheet 10 and an adherend containing a propylene resin.

The entire adherend may be formed of the resin composition. Moreover, the said adherend should just be the structure in which the area | region where the adhesive sheet 10 is laminated | stacked contains the said resin composition, for example, the said resin composition is used for the core material which consists of resin, a metal, a ceramic, etc. The structure to which the to-be-adhered body to contain may be laminated | stacked may be sufficient. The shape of the adherend is not particularly limited.

The method for laminating the adhesive sheet 10 on the adherend is not particularly limited, and methods such as lamination, vacuum forming, pressure forming, vacuum / pressure forming, in-mold forming, and film insert forming can be used. Among these, vacuum / pressure forming is preferable.

EXAMPLES Hereinafter, although an Example is hung up and demonstrated in more detail about this invention, this invention is not limited only to these Examples.

Example 1
(Preparation of polyvinyl chloride base material layer)
28 parts by weight of a plasticizer was added to 100 parts by weight of a vinyl chloride resin having an average degree of polymerization of 800 to obtain a vinyl chloride resin composition. As the vinyl chloride resin, a suspension polymer of vinyl chloride was used. The obtained polyvinyl chloride resin composition was melt-kneaded with a Banbury mixer, and then a polyvinyl chloride base material layer was produced by calendering. The film thickness of the polyvinyl chloride substrate layer was 100 μm.

(Preparation of the first primer layer)
15 parts by weight of a diluent solvent (manufactured by Konishi Co., Ltd., G thin solution) was added to and mixed with 100 parts by weight of an ethylene vinyl acetate copolymer (manufactured by Konishi Co., Ltd., KV-128). Then, using a 180 mesh gravure roll, the obtained mixed solution was applied on the polyvinyl chloride base layer so as to be 10 g / m ² and dried at 40 ° C. for 2 minutes. The thickness of the first primer layer after drying was 1 μm.

(Preparation of the second primer layer)
50 parts by weight of an ethylene vinyl acetate copolymer (KV-128, manufactured by Konishi Co., Ltd.) and 50 parts by weight of an isocyanate-based curing agent (Sumika) 5 parts by weight of Desmodur L-75 manufactured by Bayer Urethane Co., Ltd. was added and mixed to obtain a mixture of urethane resin and ethylene vinyl acetate copolymer. Then, using a 180 mesh gravure roll, the mixed solution containing the obtained mixture was applied on the first primer layer so as to be 10 g / m ² and dried at 40 ° C. for 2 minutes. The thickness of the second primer layer after drying was 1 μm.

(Lamination of hot melt adhesive layer)
On the second primer layer, a polyolefin hot-melt adhesive sheet (PPET1025, manufactured by Toagosei Co., Ltd.) having a thickness of 50 μm was adhered at 140 ° C. Thereby, the adhesive sheet laminated | stacked in order of the polyvinyl chloride base material layer, the 1st primer layer, the 2nd primer layer, and the hot-melt-adhesive agent layer was obtained.

(Example 2)
Same as Example 1 except that the compounding amount of the urethane resin in the second primer layer was changed to 40 parts by weight and the compounding amount of the ethylene vinyl acetate copolymer was changed to 50 parts by weight (compounding ratio 40:50). Thus, an adhesive sheet of Example 2 was obtained.

(Example 3)
In the first primer layer, 10 parts by weight of urethane resin (Hirono Chemical Co., Ltd., T-5265) was added to 90 parts by weight of ethylene vinyl acetate copolymer (urethane resin / ethylene vinyl acetate). Example 3 of Example 3 except that 1 part by weight of copolymerization ratio 10:90) and an isocyanate curing agent (manufactured by Sumika Bayer Urethane Co., Ltd., Desmodur L-75) were added. An adhesive sheet was obtained.

(Comparative Example 1)
An adhesive sheet of Comparative Example 1 was obtained in the same manner as in Example 1 except that the first primer layer and the second primer layer were not provided. In Comparative Example 1, after forming a polyvinyl chloride base material layer, a hot melt adhesive layer was laminated on the polyvinyl chloride base material layer to obtain an adhesive sheet.

(Comparative Example 2)
An adhesive sheet of Comparative Example 2 was obtained in the same manner as in Example 1 except that the second primer layer was not provided. In Comparative Example 2, after the polyvinyl chloride base material layer was formed, the first first primer layer was formed on the polyvinyl chloride base material layer, and hot melt was further formed on the first first primer layer. An adhesive layer was laminated to obtain an adhesive sheet.

(Comparative Example 3)
An adhesive sheet of Comparative Example 3 was obtained in the same manner as in Example 1 except that the first primer layer was not provided. In Comparative Example 3, after the polyvinyl chloride base material layer was formed, the second first primer layer was formed on the polyvinyl chloride base material layer, and hot melt was further formed on the second first primer layer. An adhesive layer was laminated to obtain an adhesive sheet.

(Comparative Example 4)
An adhesive sheet of Comparative Example 4 was obtained in the same manner as in Example 1 except that the configuration of the second primer layer was different. In Comparative Example 4, 5 parts by weight of an isocyanate-based curing agent (manufactured by Sumika Bayer Urethane Co., Ltd., Desmodur L-75) with respect to 100 parts by weight of the urethane-based resin (Hirono Chemical Industries, Ltd., T-5265) Added and mixed. Then, using a 180 mesh gravure roll, the obtained mixed solution was applied on the first primer layer so as to be 10 g / m ² and dried. The thickness of the second primer layer after drying was 1 μm. A hot melt adhesive layer was laminated on the second first primer layer to obtain an adhesive sheet.

(Comparative Example 5)
An adhesive sheet of Comparative Example 5 was obtained in the same manner as in Example 1 except that the compositions of the first primer layer and the second primer layer were changed.

In Comparative Example 5, 10 g / m ^{2 of} a mixed solution containing a mixture of the urethane resin and the ethylene vinyl acetate copolymer used in the production of the second primer layer of Example 1 on the polyvinyl chloride substrate layer. Was applied and dried at 40 ° C. for 2 minutes to prepare a first primer layer. The thickness of the first primer layer after drying was 1 μm. Subsequently, the mixed solution containing the ethylene vinyl acetate copolymer used in the production of the first primer layer of Example 1 was applied on the first primer layer so as to be 10 g / m ^2. And dried at 40 ° C. for 2 minutes to produce a second primer layer. The thickness of the second primer layer after drying was 1 μm. Thereafter, a hot melt adhesive layer was formed on the second primer layer to obtain an adhesive sheet.

(Comparative Example 6)
An adhesive sheet of Comparative Example 6 was obtained in the same manner as in Example 1 except that an acrylic resin was used for the second primer layer. In Comparative Example 6, a mixed solution containing an acrylic resin (manufactured by Nippon Shokubai Co., Ltd., Poliment NK-350), toluene, and isopropyl alcohol (IPA) was applied to the first primer layer prepared in the same manner as in Example 1. The coating was applied at 10 g / m ² and dried at 40 ° C. for 2 minutes. The thickness of the second primer layer after drying was 1 μm. Thereafter, a hot melt adhesive layer was laminated on the second first primer layer to obtain an adhesive sheet.

(Comparative Example 7)
An adhesive sheet of Comparative Example 7 was obtained in the same manner as in Example 1 except that a polyolefin-based resin was used for the second primer layer. In Comparative Example 7, a mixed liquid containing a polyolefin-based resin was applied to the first primer layer produced in the same manner as in Example 1 so as to be 10 g / m ² and dried at 40 ° C. for 2 minutes. . The thickness of the second primer layer after drying was 1 μm. Thereafter, a hot melt adhesive layer was laminated on the second first primer layer to obtain an adhesive sheet.

(Production of molded products)
The adhesive sheet of Example 1 was attached to a plate-shaped adherend made of polypropylene resin by vacuum / pressure forming to obtain a molded product. The adhesive sheets of Examples 2 and 3 and Comparative Examples 1 to 7 were also attached to a plate-shaped adherend containing a polypropylene resin in the same manner as in Example 1 to obtain molded articles.

(Evaluation of adhesive sheets and molded products)
About the adhesive sheet and molded article which were produced in the Example and the comparative example, evaluation of evaluation of (1) dimensional stability, (2) adhesive force, and (3) adhesiveness was performed by the following method. From the evaluation results of (1) to (3), (4) comprehensive evaluation was performed.

(1) Evaluation of dimensional stability The molded article which stuck the adhesive sheet of the said Example and comparative example was cut | disconnected to 150 mm long and 150 mm wide, and it was set as the test piece. A 100 mm cut was made in the flow direction and width direction with a cutter knife on the surface of the adhesive sheet of each test piece, and the sample was left in an environment of 80 ° C. for 96 hours. After 96 hours, the dimension of the adhesive sheet in the flow direction and the dimension in the width direction were measured. The target value for evaluating the dimensional stability was such that the dimensional change in the flow direction and the width direction was 0.3 mm or less. The sheet flow direction refers to the longitudinal direction of the sheet when the sheet is formed by calendering, and the width direction refers to the short direction of the sheet when the sheet is formed by calendering.

(2) Measurement of adhesive strength The molded product on which the adhesive sheets of the above Examples and Comparative Examples were attached was cut into a length of 150 mm and a width of 150 mm to obtain a test piece. Each test piece was subjected to a 180 ° peel test to measure the adhesive force. Evaluation was performed by a method based on JIS Z 0237. If the target value of the adhesive force was 30 N / 25 mm or more, it was judged that the adhesive force was sufficient.

(3) Evaluation of adhesion The molded product on which the adhesive sheets of the above examples and comparative examples were attached was cut into a length of 150 mm and a width of 150 mm to obtain a test piece. The adhesive sheet is peeled off from each test piece, the peeled interface is visually observed, and the adhesive strength to the adherend (PO resin) containing the polyvinyl chloride base layer (PVC resin) and the polypropylene resin is measured. evaluated. Delamination occurs between the adherend containing the polypropylene resin and the hot melt adhesive layer, and there is adhesion between the polyvinyl chloride base material layer and the hot melt adhesive layer constituting the adhesive sheet. When it was kept, it was set as ○. When delamination occurs between the polyvinyl chloride base material layer and the hot melt adhesive layer constituting the adhesive sheet, and the hot melt adhesive layer remains on the adherend containing the polypropylene resin, x and did.

(4) Comprehensive evaluation If all the evaluation items (1) to (3) satisfy the target value, ○, and if there are one or more items that deviate from the target values of the evaluation items (1) to (3), × did.

Tables 1 and 2 show the configurations and evaluation results of the adhesive sheets of Examples and Comparative Examples. In addition, only the structure of the primer layer was described as a structure of an adhesive sheet.

10 Adhesive Sheet 11 Polyvinyl Chloride Base Layer 12 First Primer Layer 13 Second Primer Layer 14 Hot Melt Adhesive Layer

Claims (4)

Laminated in the order of a polyvinyl chloride base layer, a first primer layer, a second primer layer, and a hot melt adhesive layer,
The first primer layer contains an ethylene vinyl acetate copolymer,
The second primer layer contains a mixture of urethane resin and ethylene vinyl acetate copolymer,
The hot melt adhesive layer contains a polyolefin-based resin. In the mixture of the urethane resin and the ethylene vinyl acetate copolymer, the ratio of the blending amount (parts by weight) of the urethane resin and the blending amount (parts by weight) of the ethylene vinyl acetate copolymer is 30:70. It is -70: 30, The adhesive sheet of Claim 1 characterized by the above-mentioned. The adhesive sheet according to claim 1, wherein the adhesive sheet is a decorative adhesive sheet. A molded product comprising the adhesive sheet according to any one of claims 1 to 3 and an adherend containing a polycarbonate resin, acrylonitrile / butadiene / styrene resin, or polyolefin resin.

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