JP2005154507A - Resin composition and resin sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which contains amorphous polyethylene terephthalate and can form a resin sheet through calendering, wherein the resin sheet achieves sufficient softening, is excellent in heat-blocking resistance and tear strength, and sufficiently inhibits reduction in elongation over time, and the resin sheet made of the resin composition. <P>SOLUTION: The resin composition contains a resin component comprising the amorphous polyethylene terephthalate and an acrylic resin, wherein the contents of the amorphous polyethylene terephthalate and the acrylic resin are 40-85 wt.% and 15-60 wt.%, respectively, against the total weight of the resin component. The acrylic resin is a polymer particle having a multilayered structure which has a rubber layer inside and a thermoplastic resin layer in the outermost. The acrylic resin shows a winding speed of ≥20 mm/min and tension of 20-70 mN. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a resin composition containing amorphous polyethylene terephthalate and a resin sheet made of the resin composition.

  Polyethylene terephthalate sheets (films) are used in various applications such as packaging materials for foods and pharmaceuticals, and sheets for lamination of buildings and home appliances. Conventionally, polyethylene terephthalate sheets used for such applications are generally formed by extrusion molding or injection molding.

  However, in these molding methods, it takes time to change the product type and it is difficult to form a continuous sheet, and the productivity is not sufficient.

  In contrast to these forming methods, a calendering method generally used as a sheet forming method for polyvinyl chloride or the like is a method in which a molten resin is rolled with a heated metal roll to form a sheet having a desired thickness. Therefore, it is relatively easy to handle widths and change varieties, and it is suitable for forming continuous sheets, so that high productivity can be obtained. When such a calendering method is applied, as the material, amorphous polyethylene terephthalate, which is superior in processability than ordinary polyethylene terephthalate, is used.

  However, when amorphous polyethylene terephthalate is used alone as the resin component, it is difficult to adjust the hardness, and it is difficult to obtain a semi-rigid sheet suitable for applications such as stickers. In addition, a sheet formed by using amorphous polyethylene terephthalate alone as a resin component has a problem in that the heat blocking resistance is insufficient and the elongation significantly decreases with time.

In addition, as a resin composition and sheet using non-crystalline polyethylene terephthalate and another resin as a resin component, (meth) acrylic acid ester or (meth) acrylic acid ester is added to conjugated diene rubber particles as the other resin. A resin composition and a sheet using a graft copolymer obtained by graft polymerization of vinyl aromatic with vinyl are proposed (see Patent Documents 1 and 2).
JP 2001-247753 A International Publication No. 99/40154 Pamphlet

  However, in the resin composition and sheet using amorphous polyethylene terephthalate and the above graft copolymer as the resin component, it is difficult to make both the sheet softening and heat blocking resistance sufficient. In some cases, a problem arises in the tear strength of the sheet.

  The present invention has been made in view of the above-described problems of the prior art. Softening has been sufficiently achieved, heat blocking resistance and tear strength are excellent, and a decrease in elongation over time is sufficiently suppressed. Another object of the present invention is to provide a non-crystalline polyethylene terephthalate-containing resin composition capable of forming the resin sheet by calendering, and a resin sheet comprising the resin composition.

  As a result of intensive studies to achieve the above object, the present inventors have sufficiently achieved softening by using amorphous polyethylene terephthalate and a specific acrylic resin in a specific ratio as resin components. In addition, the present inventors have found that a resin composition capable of forming a resin sheet excellent in heat-resistant blocking property and tear strength and capable of forming a resin sheet in which a decrease in elongation with time is sufficiently suppressed can be obtained by calendering. It came.

  That is, the present invention is a resin composition containing a resin component comprising amorphous polyethylene terephthalate and an acrylic resin, and the content of the amorphous polyethylene terephthalate is based on the total weight of the resin component. 40 to 85% by weight, acrylic resin content is 15 to 60% by weight, the acrylic resin has a rubber layer made of a copolymer of an acrylate ester and a copolymer monomer inside, and a methacrylate ester Is a multilayer structure polymer particle having a thermoplastic resin layer made of a polymer containing as a monomer unit on the outermost part, and an acrylic resin by a capillary rheometer provided with a capillary having an inner diameter of 1.00 mm and a length of 10.00 mm. When the coil was wound at an increased speed while flowing out at a furnace temperature of 185 ° C. and a piston speed of 10 mm / min, Winding speed of 20 mm / min or more during the break, and that the tension is 20～70MN, to provide a resin composition characterized.

  According to such a resin composition, by using a multilayer structure polymer particle having a rubber layer and a thermoplastic resin layer as an acrylic resin, the winding speed at break and the tension being in the specific range, Amorphous polyethylene terephthalate can be sufficiently softened, and heat blocking resistance and tear strength are superior compared to the case of using amorphous polyethylene terephthalate alone and the case of using the above acrylic resin alone. Therefore, calendar workability can be improved, a decrease in elongation over time can be sufficiently suppressed, and a resin sheet having a uniform thickness and a desired hardness can be obtained.

  Here, the “sheet” in the present invention includes a sheet and a film.

  Further, in the acrylic resin contained in the resin composition of the present invention, the copolymerization monomer is composed of a polyfunctional copolymerization monomer and a monofunctional copolymerization monomer contained as necessary, and the rubber layer comprises A copolymer of 50 to 99.99% by weight of an acrylic ester, 0.01 to 10% by weight of a polyfunctional copolymer monomer, and 0 to 49.99% by weight of a monofunctional copolymer monomer It is preferable that

  Furthermore, in the acrylic resin contained in the resin composition, the multi-layered polymer particles preferably comprise 30 to 90% by weight of a rubber layer and 10 to 70% by weight of a thermoplastic resin layer.

  By using such an acrylic resin, the calender processability of the resin composition can be improved, softening is achieved more sufficiently, heat blocking resistance and tear strength are more excellent, and It is possible to form a resin sheet in which a decrease in elongation over time is more sufficiently suppressed.

  Furthermore, the resin composition further contains 0.1 to 4 parts by weight of a lubricant component with respect to 100 parts by weight of the resin component, and the lubricant component contains 0.01 to 1 part by weight of an olefin wax and a fatty acid ester. It is preferable to contain 0.01-0.5 weight part and 0.01-2.5 weight part of calcium salt of fatty acid ester.

  A resin composition containing such a lubricant component can drastically improve roll lubricity and anti-plate-out property in calendering while maintaining good printability when formed into a resin sheet.

  The present invention also provides a resin sheet characterized by calendering the above resin composition of the present invention.

  Such a resin sheet provides excellent heat blocking resistance and tear strength, and sufficiently suppresses a decrease in elongation over time. Furthermore, since this resin sheet is also excellent in printability, it can be applied to applications such as stickers that require semi-rigidity and printability.

  According to the present invention, it is possible to form a resin sheet in which softening is sufficiently achieved, heat blocking resistance and tear strength are excellent, and a decrease in elongation over time is sufficiently suppressed. An excellent resin composition can be provided. Further, it is possible to provide a resin sheet comprising the above resin composition, which is sufficiently softened and excellent in heat-resistant blocking property, in which a decrease in elongation with time is sufficiently suppressed, and further excellent in printability. it can.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof. In the following description, (meth) acrylic acid means acrylic acid or methacrylic acid corresponding to it, and (meth) acrylate means acrylate or methacrylate corresponding thereto.

  First, the resin composition of the present invention will be described.

  The resin composition of the present invention is a resin composition containing a resin component comprising amorphous polyethylene terephthalate and an acrylic resin, and the amorphous polyethylene terephthalate is based on the total weight of the resin component. The content of the acrylic resin is 15 to 60% by weight, and the acrylic resin contains a rubber layer made of a copolymer of an acrylate ester and a copolymerization monomer inside. A multilayer structure polymer particle having a thermoplastic resin layer made of a polymer containing a methacrylic acid ester as a monomer unit on the outermost part, and the acrylic resin is a capillary having an inner diameter of 1.00 mm and a length of 10.00 mm With a capillary rheometer equipped with a furnace temperature of 185 ° C and a piston speed of 10 mm / min. If you, the winding speed at break of leaked resin is 20 mm / min or more, the tension is 20～70MN, is characterized in.

  Here, the non-crystalline polyethylene terephthalate in the present invention includes a dicarboxylic acid component composed of 100 mol% terephthalic acid, and a glycol component composed of 60 to 80 mol% ethylene glycol and 20 to 40 mol% 1,4-cyclohexanedimethanol. It is a copolymer.

  Further, the acrylic resin in the present invention has a rubber layer made of a copolymer of an acrylate ester and a copolymerizable monomer inside, and a thermoplastic resin layer made of a polymer containing methacrylic acid ester as a monomer unit on the outermost side. It consists of multi-layer structured polymer particles.

  The multi-layer structured polymer particles are composed of two or more layers having at least one rubber layer inside and at least the thermoplastic resin layer as an outermost layer (so-called core-shell structure). And the number of layers may be three or four or more.

  In the case of a two-layer structure, the rubber layer is the central layer, and the outer layer (outermost layer) around it is the thermoplastic resin layer. In the case of a three-layer structure, it consists of a central layer, an intermediate layer, and an outermost layer, at least the central layer is a rubber layer, and the outermost layer is a thermoplastic resin layer. Further, the intermediate layer may be either a rubber layer or a thermoplastic resin layer, but the intermediate layer between the center layer and the outermost layer has a smaller rubber component than the center layer to increase the proportion of the thermoplastic resin. It is preferable that it is a resin layer.

  Therefore, in a multilayer structure of two or more layers, at least the center layer may be a rubber layer and the outermost layer may be a thermoplastic resin layer, and the other layer may be either a rubber layer or a thermoplastic resin layer, It is preferable to have a layer structure in which the ratio of the rubber component and the thermoplastic resin is gradually changed.

  Moreover, the weight of the rubber layer (the total weight when there are a plurality of layers) is 30 to 90% by weight, based on the weight of the entire multilayer structure polymer particle, and the weight of the thermoplastic resin layer (when there are a plurality of layers) Is preferably 10 to 70% by weight. If the weight of the rubber layer is less than 30% by weight, softening of the resin sheet to be formed tends to be insufficient, and if the weight of the thermoplastic resin layer is less than 10% by weight, the layer structure (particularly the outermost layer) ) Is insufficient, and therefore melt flowability tends to decrease and processability tends to be insufficient.

  The rubber layer is a polymer layer having rubber elasticity composed of a copolymer of an acrylate ester and a copolymerizable monomer copolymerizable with the acrylate ester. Here, the copolymerization monomer is another multifunctional copolymerizable monomer copolymerizable with the acrylate ester and other monofunctional copolymer copolymerizable with the acrylate ester contained as necessary. The rubber layer is made of a monomer, and the rubber layer has an acrylic ester of 50 to 99.99% by weight, a polyfunctional copolymer monomer of 0.01 to 10% by weight, and a monofunctional copolymer monomer of 0 to 49.99% by weight. The polymer layer is preferably made of a copolymer of.

  If the acrylic ester content is less than 50% by weight, the rubber elasticity of the rubber layer is lowered, and accordingly, the rubber elasticity of the multilayer polymer particles is lowered, and the resin sheet to be formed is insufficiently softened. When the content exceeds 99.99% by weight, the structure of the multilayer polymer particles tends to be difficult to be formed. On the other hand, if the content of the monofunctional copolymerization monomer exceeds 49.99% by weight, the weather resistance of the multilayer structure polymer particles tends to be insufficient. Furthermore, when the content of the polyfunctional copolymerization monomer is less than 0.01% by weight, the structure of the multilayer structure polymer particles tends to be difficult to be formed. When the content exceeds 10% by weight, the rubber elasticity of the rubber layer is increased. As a result, the rubber elasticity of the multi-layered polymer particles decreases, and the softening of the resin sheet to be formed tends to be insufficient.

  Examples of the acrylic ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, s-butyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, Examples include acrylic acid alkyl esters such as 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, and octadecyl acrylate; esters of acrylic acid such as phenyl acrylate and phenols; esters of acrylic acid such as benzyl acrylate and aromatic alcohols, and the like. . These can be used alone or in combination of two or more.

  The polyfunctional copolymer monomer is a monomer having two or more carbon-carbon double bonds in the molecule. For example, unsaturated carboxylic acid such as acrylic acid, methacrylic acid, cinnamic acid, allyl alcohol, and methallyl alcohol. And an unsaturated alcohol such as ethylene glycol and butanediol; an ester of a dicarboxylic acid such as phthalic acid, terephthalic acid, isophthalic acid, and maleic acid and the unsaturated alcohol. More specifically, for example, allyl acrylate, methallyl acrylate, allyl methacrylate, methallyl methacrylate, allyl cinnamate, methallyl cinnamate, diallyl maleate, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, divinylbenzene , Ethylene di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and the like. Among these polyfunctional copolymerization monomers, allyl methacrylate is particularly preferable. These can be used alone or in combination of two or more.

  The monofunctional copolymerization monomer is a monomer that is used as necessary. For example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl Methacrylic acid alkyl esters such as methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, myristyl methacrylate, palmityl methacrylate, stearyl methacrylate, behenyl methacrylate, and octadecyl methacrylate; esters of methacrylic acid such as phenyl methacrylate and phenols; benzyl methacrylate Methacrylic acid and aromatic al Methacrylic acid esters such as esters with alcohol are typical, but other examples include styrene, α-methylstyrene, 1-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4- Aromatic vinyl monomers such as dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, halogenated styrene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; butadiene, isoprene, 2, 3-dimethylbutadiene, 2-methyl-3-ethylbutadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 2-ethyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl- 1,3-hexadiene, 3,4-dimethyl-1,3-hexadiene, 1,3 -Conjugated diene monomers such as heptadiene, 3-methyl-1,3-heptadiene, 1,3-octadiene, cyclopentadiene, chloroprene, and myrcene. These can be used alone or in combination of two or more.

  The thermoplastic resin layer is a polymer layer having thermoplasticity made of a polymer containing methacrylic acid ester as a monomer unit. Further, the polymer constituting the thermoplastic resin layer may contain a copolymerizable monomer copolymerizable with the methacrylic acid ester as a monomer unit within the range not impairing the effects of the present invention. The content of the polymerization monomer is preferably 40% by weight or less based on the total amount of the polymer. When the content exceeds 40% by weight, light resistance and calendar workability tend to be insufficient.

  Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, myristyl. Examples include methacrylate, palmityl methacrylate, stearyl methacrylate, behenyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate, and the like, preferably methyl methacrylate. These can be used alone or in combination of two or more.

  Examples of the copolymerizable monomer copolymerizable with the methacrylic acid ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, s-butyl acrylate, t-butyl acrylate, pentyl acrylate, Acrylic acid alkyl esters such as hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate; styrene, α-methylstyrene, 1-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4- Cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, Aromatic vinyl monomers such as genated styrene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, Examples thereof include maleimide monomers such as N-cyclohexylmaleimide, N-phenylmaleimide, N- (p-bromophenyl) maleimide and N- (chlorophenyl) maleimide; the polyfunctional copolymerization monomers described above. Among these, acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, and n-butyl acrylate are preferable. These can be used alone or in combination of two or more.

  Further, the number average molecular weight of the polymer constituting the thermoplastic resin layer measured by GPC (gel permeation chromatography) method is preferably 30,000 or less, and is 1,000 to 30,000. More preferably, it is more preferably 3,000 to 20,000. When the number average molecular weight exceeds 30,000, the melt fluidity tends to be lowered and the processability tends to be insufficient, and the softening of the resin sheet to be formed tends to be insufficient. In addition, when two or more thermoplastic resin layers are included in the multilayer structure polymer, it is preferable that at least the outermost thermoplastic resin layer satisfies the above conditions, and all the thermoplastic resin layers are It is more preferable that the above condition is satisfied.

  Such multilayer structure polymer particles including a rubber layer and a thermoplastic resin layer form, for example, a polymerization reaction step for forming a rubber layer and a polymerization reaction step for forming a thermoplastic resin layer. By carrying out in the order corresponding to the layer structure of the multi-layered polymer particles, it can be obtained by sequentially forming layers from the center to the outside.

  Here, as a polymerization method for forming each layer, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a solution polymerization method, or a combination thereof can be employed.

  The average particle size of the multilayered polymer particles thus obtained is preferably 150 nm or less, and more preferably 30 to 150 nm. When the average particle diameter exceeds 150 nm, the melt fluidity tends to decrease and the calenderability tends to be insufficient, and the softening of the resin sheet to be formed tends to be insufficient.

  The acrylic resin according to the present invention composed of the multilayer structure polymer particles described above is a furnace rheometer temperature of 185 ° C. and a piston speed of 10 mm / min by a capillary rheometer provided with a capillary having an inner diameter of 1.00 mm and a length of 10.00 mm. When the acrylic resin is allowed to flow out and the flowed resin is wound at an increased speed, the winding speed at the time of breakage of the flowed resin is 20 mm / min or more and the tension is 20 to 70 mN.

  Here, “winding speed” and “tension” in the present invention are measured as follows.

  First, in accordance with JIS K 7199 “Method for testing flow characteristics of thermoplastics with capillary rheometer”, a capillary rheometer having a furnace body diameter of 9.55 mm equipped with a capillary with an inner diameter of 1.00 mm and a length of 10.00 mm is acrylic. After filling the resin and setting the furnace temperature to 185 ° C. to bring the resin into a molten state, the acrylic resin is caused to flow out from the capillary into a thin line at a piston speed of 10 mm / min. While performing this outflow, the acrylic resin (hereinafter referred to as “thin line resin”) that has flowed out into a thin line is wound up at a constant speed by a winder while increasing the winding speed. Here, for the winding, the capilograph 1C accessory (manufactured by Toyo Seiki Seisakusho) is used, and the winding is started in a state where the thin linear resin is not slack, and the winding speed is from 0 mm / min to 199.9 mm. / Time is set to 10 minutes, and the winding is accelerated at a constant acceleration. Thus, the high-speed winding of the fine linear resin is performed, and the winding speed (limit speed) when the fine linear resin is broken is measured. Furthermore, the tension (maximum tension) when the thin linear resin is broken is measured.

  Here, as a capillary rheometer, Capillograph 1C (made by Toyo Seiki Seisakusho) was used.

  The winding speed measured in this manner indicates the characteristics of the molten polymer. The larger this value, the better the workability that can be obtained in calendaring with stretching.

  The acrylic resin according to the present invention needs to have a winding speed of 20 mm / min or more. When the winding speed is less than 20 mm / min, it is difficult to perform stable stretching, and the workability at the time of calendering becomes insufficient.

  Further, the tension measured as described above indicates the characteristics of the molten polymer, and the larger this value, the easier it is to take it out in calendering.

  The acrylic resin according to the present invention is required to have a tension of 20 to 70 mN, and preferably 20 to 60 mN. When the tension is less than 20 mN, the workability at the time of calendering becomes insufficient due to drawdown or the like, and when it exceeds 70 mN, the workability at the time of calendering becomes insufficient, for example, the load at the time of calendering becomes large.

  The resin composition of the present invention includes a resin component composed of the above-described amorphous polyethylene terephthalate and acrylic resin, and the content of the amorphous polyethylene terephthalate is 40 to 85 based on the total weight of the resin component. The content of acrylic resin is 15 to 60% by weight. Moreover, it is preferable that content of an amorphous polyethylene terephthalate is 50 to 80 weight%, and it is more preferable that it is 60 to 75 weight%. On the other hand, the content of the acrylic resin is preferably 20 to 50% by weight, and more preferably 25 to 40% by weight.

  When the content of the amorphous polyethylene terephthalate is less than 40% by weight, the tear strength of the formed resin sheet is remarkably lowered, and it becomes difficult to apply it to a use as a PVC substitute sheet, such as a sticker. . Moreover, when content of an amorphous polyethylene terephthalate exceeds 85 weight%, the softening of the formed resin sheet, the improvement of heat-resistant blocking property, and suppression of the fall of elongation with time will become inadequate.

  In addition, the resin composition concerning this invention may contain other resins other than the said amorphous polyethylene terephthalate and the said acrylic resin, as long as the effect of this invention is not impaired. In this case, the content of the other resin is preferably 30% by weight or less with respect to 100 parts by weight of the total weight of the amorphous polyethylene terephthalate and the acrylic resin. However, from the viewpoint of obtaining the effects of the present invention more reliably, it is most preferable not to include other resins.

  The resin composition of the present invention is an acrylic resin containing the multilayer structure polymer described above, and contains a specific amount of the acrylic resin having the winding speed and tension described above together with the amorphous polyethylene terephthalate. Therefore, excellent calenderability can be obtained, and when molded into a resin sheet, softening of the sheet, improvement of heat-resistant blocking property and tear strength, and suppression of decrease in elongation over time are sufficiently achieved. Can do.

  The resin composition of the present invention preferably further contains a lubricant component in addition to the resin component, and the lubricant component includes an olefinic wax, a fatty acid ester, a calcium salt of the fatty acid ester, It is preferable that it contains.

  Examples of the olefin wax include polyethylene wax, polypropylene wax, and polybutylene wax. From the viewpoint of improving calendar processability such as roll lubricity, the number average molecular weight is 50,000 or less. A polyolefin wax is preferable, and a polyolefin wax having a number average molecular weight of 30,000 or less is more preferable. Among the above-mentioned polyolefin waxes, modified polyolefin waxes containing carboxylic acid groups and hydroxyl groups in the molecule by a method such as oxidation, or containing unsaturated groups by reacting maleic acid or epoxy group-containing compounds, etc. Preferably, the acid value by the measuring method described in JIS K 5902 is more preferably 10 or more. By using such an olefin-based wax, there is a tendency that roll lubricity at the time of calendering is improved. In the present invention, such olefin waxes can be used alone or in combination of two or more.

  Examples of the fatty acid ester include a synthetic wax composed of an ester of a fatty acid and an aliphatic alcohol, or a natural wax. The fatty acid is preferably a saturated fatty acid having 20 to 30 carbon atoms, such as behenic acid, Examples include lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid and the like. In the present invention, montanic acid is particularly preferable. By using such a fatty acid, the roll lubricity at the time of calendar processing tends to be improved. The aliphatic alcohol is preferably an aliphatic saturated alcohol having 2 to 35 carbon atoms, and examples thereof include octyl alcohol, stearyl alcohol, lauryl alcohol, ethylene glycol, and glycerin. Examples of fatty acid esters composed of such fatty acids and fatty alcohols include, for example, synthetic waxes such as octyl behenate, stearyl behenate, lauryl behenate, ceryl serotic ester, and montanic acid glycol ester, montan wax, Examples thereof include natural waxes such as carnauba wax and beeswax. In the present invention, it is particularly preferable to use montanic acid glycol ester and montan wax. By using such a fatty acid ester, the kneading operation with the resin tends to be easy. In this invention, such fatty acid ester can be used individually or in combination of 2 or more types.

  Examples of the calcium salt of the fatty acid ester include salts of the fatty acid ester and calcium as described above, and the fatty acid comprising the saturated fatty acid having 20 to 30 carbon atoms and the aliphatic saturated alcohol having 2 to 35 carbon atoms as described above. It is preferably a salt of ester and calcium. In the present invention, it is particularly preferable to use a calcium salt of montanic acid glycol ester. By using such a calcium salt of a fatty acid ester, the appearance and various physical properties of the resulting resin sheet can be improved, and the roll lubricity during calendering tends to be improved. In the present invention, such calcium salts of fatty acid esters can be used alone or in combination of two or more.

  The resin composition of the present invention preferably contains 0.1 to 4 parts by weight, preferably 0.5 to 2 parts by weight, of the above-mentioned three types of lubricant component containing 100 parts by weight of the resin component. More preferably. When the blending amount of the lubricant is less than 0.1 parts by weight, the improvement of the roll lubricity during calendering tends to be insufficient, and when it exceeds 4 parts by weight, a plate-out occurs during processing. It tends to become dull, and the printability of the resulting resin sheet tends to decrease.

  The blending amount of the olefin wax is preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the resin component within the range of blending amount as the total amount of the lubricant component, and 0.1 to 0. More preferably, it is 5 parts by weight. When the blending amount is less than 0.01 parts by weight, the improvement of the roll lubricity at the time of calendering tends to be insufficient, and when it exceeds 1 part by weight, plate-out is likely to occur during processing. There is a tendency.

  Further, the blending amount of the fatty acid ester is preferably 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the resin component within the range of blending amounts as the total amount of the lubricant component, More preferably, it is 0.4 parts by weight. If the blending amount is less than 0.01 parts by weight, the improvement in roll lubricity at the time of calendar processing tends to be insufficient, and if it exceeds 0.5 parts by weight, the printability of the resulting resin sheet Tend to decrease.

  Furthermore, the blending amount of the calcium salt of the fatty acid ester is preferably 0.01 to 2.5 parts by weight with respect to 100 parts by weight of the resin component, within the range of the blending amount as the total amount of the lubricant component. More preferably, it is 0.1 to 1 part by weight. If the blending amount is less than 0.01 parts by weight, the improvement in roll lubricity during calendering tends to be insufficient, and if it exceeds 2.5 parts by weight, plate-out occurs during processing. It tends to be easier.

  The resin composition of the present invention contains the above-described amorphous polyethylene terephthalate and acrylic resin as resin components, and also contains the above-mentioned lubricant component, thereby softening the sheet when molded into a resin sheet. In addition, it is possible to sufficiently improve the heat blocking resistance and tear strength, as well as to suppress the decrease in elongation over time, and to improve the slipperiness and anti-plate-out properties during calendering and the printability of the resin sheet. It can be excellent.

  Further, in the resin composition of the present invention, other general lubricants other than the above three types may be further used as the lubricant component. In this case, the amount of the other lubricant is based on 100 parts by weight of the resin component. And preferably 1.5 parts by weight or less.

  Further, the resin composition of the present invention includes, in addition to the above components, an antioxidant, a weathering agent, an antistatic agent, a processing aid, a colorant such as a silicone oil, a dye or a pigment, An additive such as a filler such as calcium and a flame retardant can be added as long as the effects of the present invention are not impaired. The blending amount of such an additive is preferably 30 parts by weight or less with respect to 100 parts by weight of the resin component.

  Next, the resin sheet of the present invention will be described.

  The resin sheet of the present invention is obtained by calendering the resin composition of the present invention as described above.

  Here, the calendering is performed, for example, by kneading the resin composition using a calendering machine and processing it into a sheet shape. In addition, after mixing the said resin composition previously with a Banbury etc., you may knead | mix and calender using a calendering machine. Moreover, what is necessary is just a calendering machine provided with two or more metal rolls as a calendering machine, and it is preferable to calender at 170-190 degreeC as roll surface temperature.

  In addition, the method of using the resin sheet of the present invention is not particularly limited, but it can be used for applications that require semi-rigidity, such as sticker sheets and marking sheets.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

(Examples 1-4, Comparative Examples 1-10)
The components shown in Table 1 and Table 2 are blended in the amounts (parts by weight) shown in the same table, and these are melt-kneaded for about 10 minutes at a temperature range of 90 to 160 ° C. with a Banbury mixer, and then using a calendar processing machine. Then, calendering was performed at a roll surface temperature of 185 ° C. to obtain a resin film having a thickness of 0.1 mm and a width of 1,200 mm. However, in Comparative Example 6, a film could not be formed because the melt tension of the resin was too high.

In addition, as various components shown in Table 1 and Table 2, the following were used specifically.
Amorphous polyethylene terephthalate: TSUNAMI GS-2 (manufactured by Eastman Chemical Co., Ltd., dicarboxylic acid component: terephthalic acid 100 mol%, glycol component: ethylene glycol 70 mol%, 1,4-cyclohexanedimethanol 30 mol%);
Acrylic resin A: Parapet SA1000-F10 (manufactured by Kuraray Co., Ltd., three-layer polymer particles, inner layer (center layer): acrylic rubber component, outermost layer: thermoplastic resin component not containing aromatic vinyl monomer, at break Winding speed: 54 mm / min, tension: 47 mN);
Acrylic resin B: Metabrene P530A (Mitsubishi Rayon Co., Ltd., a copolymer of methyl methacrylate and alkyl acrylate, weight average molecular weight: 3,100,000, the winding speed and tension at the time of rupture show that the resin is hard and flows out. Measurement was not possible due to the failure)
Acrylic resin C: Metabrene W-300A (manufactured by Mitsubishi Rayon Co., Ltd., polymer particles obtained by graft polymerization of (meth) acrylic acid ester and vinyl aromatic to acrylic rubber particles, winding speed at break: 2 mm / min, Tension: 176 mN);
Acrylic resin D: Kane Ace B-56 (manufactured by Kaneka Chemical Co., Ltd., polymer particles obtained by graft polymerization of acrylate ester and vinyl aromatic to conjugated diene rubber particles, winding speed at break: 5 mm / min, tension : 174 mN);
Olefin wax: Polyethylene oxide wax;
Calcium salt of fatty acid ester: montanic acid ethylene glycol ester calcium salt;
Fatty acid ester: Montanic acid ethylene glycol ester.

[Evaluation of softening]
10 parts by weight of a plasticizer (DOP) was added to 100 parts by weight of polyvinyl chloride, and melt kneading and calendering were performed in the same manner as in Example 1 to obtain a PVC film A having a thickness of 0.1 mm. Similarly, PVC film B was obtained from 100 parts by weight of polyvinyl chloride and 40 parts by weight of a plasticizer.

The PVC films A and B thus obtained were used to indicate the degree of softening of the resin films obtained in Examples 1 to 4 and Comparative Examples 1 to 5 and 7 to 10 based on the following evaluation criteria. I touched it. The results are shown in Tables 1 and 2.
Evaluation criteria for softening:
○: The degree of softening between the PVC film A and the PVC film B Δ: Slightly harder than the PVC film A, but softening is felt ×: Harder than the PVC film A, and softening is not felt

[Evaluation of heat-resistant blocking properties]
From the resin films obtained in Examples 1 to 4 and Comparative Examples 1 to 5 and 7 to 10, two square films each having a 6 cm square were cut out, the two films were stacked and sandwiched between glass plates, and a 1 kg weight. And left in an oven at 80 ° C. for 4 hours. At this time, the degree of close contact between the films was determined based on the following evaluation criteria. The results are shown in Tables 1 and 2.
Heat blocking resistance evaluation criteria:
○: Easily peelable △: Feels close, but peelable

[Evaluation of decrease in elongation over time]
The resin films obtained in Examples 1 to 4 and Comparative Examples 1 to 5 and 7 to 10 were left in an oven at 50 ° C. for 1 week, and the reduction rate of the elongation at break of the resin film before and after being left was determined. Evaluation was performed based on the evaluation criteria. The results are shown in Tables 1 and 2.
Evaluation criteria for elongation decrease over time:
○: Reduction rate is less than 10% △: Reduction rate is 10% or more and less than 20% ×: Reduction rate is 20% or more

[Evaluation of calendar workability]
In Examples 1 to 4 and Comparative Examples 1 to 5 and 7 to 10, the ease of adjusting the interval between rolls was evaluated based on the following evaluation criteria from the degree of roll closure when forming a resin film by calendering. . The results are shown in Tables 1 and 2.
Processability evaluation criteria:
○: Resin rebound is appropriate and roll interval adjustment can be performed smoothly. Δ: Resin rebound is slightly large and roll interval adjustment is difficult. ×: Resin rebound is large and roll interval adjustment is difficult.

[Evaluation of tear strength]
For the resin films obtained in Examples 1 to 4 and Comparative Examples 1 to 5 and 7 to 10, the test speed was measured by a right-angled tearing method in accordance with JIS K 7128 “Plastic film and sheet tearing test method”. The load and tear strength during transverse tearing were measured at 200 mm / min and evaluated based on the following evaluation criteria. The results are shown in Tables 1 and 2.
Tear strength evaluation criteria:
○: Tear strength is 100 N / mm or more Δ: Tear strength is 60 N / mm or more and less than 100 N / mm ×: Tear strength is less than 60 N / mm

[Evaluation of printability]
After the resin films obtained in Examples 1 to 4 and Comparative Examples 1 to 5 and 7 to 10 were promoted for one week at a temperature of 40 ° C. and a humidity of 80%, printing ink for PVC sheets (Nagase Screen Printing Research) Vineate (for scale) manufactured by Tokoro, diluted with a solvent (toluene / MIBK = 1/1) and prepared so that the kinematic viscosity at 18 ° C. becomes 490 mPa · S) is about 10 μm thick using a Meyer bar. The coating was made by removing the solvent by drying at room temperature for 24 hours. After that, in accordance with the cross-cut method specified in JIS K 5600, a cut-like cut is made on the coating film, an adhesive tape is pasted thereon, and the adhesion state of the coating film after peeling the adhesive tape Evaluated. As a result, the resin films obtained in Examples 1 to 4 have better coating adhesion and excellent printability than the resin films obtained in Comparative Examples 1 to 5 and 7 to 10. It was confirmed that

Claims (5)

A resin composition comprising a resin component comprising amorphous polyethylene terephthalate and an acrylic resin,
Based on the total weight of the resin component, the content of the amorphous polyethylene terephthalate is 40 to 85% by weight, the content of the acrylic resin is 15 to 60% by weight,
A multilayer structure in which the acrylic resin has a rubber layer made of a copolymer of an acrylate ester and a copolymerization monomer inside, and has a thermoplastic resin layer made of a polymer containing methacrylic acid ester as a monomer unit inside. Polymer particles,
When the acrylic resin was wound at an increased speed while flowing out at a furnace temperature of 185 ° C. and a piston speed of 10 mm / min by a capillary rheometer equipped with a capillary having an inner diameter of 1.00 mm and a length of 10.00 mm, the discharged resin A resin composition characterized by having a winding speed at break of 20 mm / min or more and a tension of 20 to 70 mN. The copolymerization monomer is composed of a polyfunctional copolymerization monomer and a monofunctional copolymerization monomer contained as necessary,
The rubber layer comprises 50 to 99.99% by weight of the acrylic ester, 0.01 to 10% by weight of the polyfunctional copolymer monomer, 0 to 49.99% by weight of the monofunctional copolymer monomer, The resin composition according to claim 1, wherein the resin composition comprises:   3. The resin composition according to claim 1, wherein the multilayer structure polymer particle is composed of 30 to 90% by weight of the rubber layer and 10 to 70% by weight of the thermoplastic resin layer. Further containing 0.1 to 4 parts by weight of a lubricant component with respect to 100 parts by weight of the resin component,
The lubricant component comprises 0.01 to 1 part by weight of an olefin wax, 0.01 to 0.5 part by weight of a fatty acid ester, and 0.01 to 2.5 parts by weight of a calcium salt of the fatty acid ester; The resin composition as described in any one of Claims 1-3 characterized by these. A resin sheet obtained by calendering the resin composition according to any one of claims 1 to 4.