JP2022100092A - Modifier for resin sheets, polyester resin composition, polyester resin sheet, laminated sheet and method for producing molding - Google Patents

Abstract

To provide a modifier that is used in combination with a polyester resin and gives a resin sheet having excellent surface slipperiness without impairing its transparency, and a polyester resin composition comprising the same, a polyester resin sheet, a laminated sheet, and a method for producing a molding.SOLUTION: The inventive modifier for resin sheets is used for producing resin sheets and contains (A) an ester compound of a tri- to hexa-valent polyhydric alcohol and a fatty acid having a C8-22 hydrocarbon group and (B) a compound having calcium element, with the content of the calcium element being 0.1-3.0 mass% relative to the modifier.SELECTED DRAWING: None

Description

The present invention is a modifier used for producing a polyester resin sheet having excellent transparency and surface slipperiness, and a method for producing a polyester resin composition containing the same, a polyester resin sheet, a laminated sheet, and a molded product. Regarding.

A film or sheet made of a polyester resin typified by polyethylene terephthalate (PET) has excellent transparency and can be easily bent, punched and cut. Therefore, for example, the film or sheet is thermoformed. Foods, chemicals, stationery, containers for various parts, lid products, etc. are manufactured by using the product. When these molded bodies are manufactured, they are adjusted to a predetermined width and length, and are supplied to the thermoforming apparatus one by one from a pile of polyester sheets in which a large number of sheets are stacked and processed. However, if the slipperiness of the sheet is not sufficient or the sheet is blocked, a defective product may be obtained or the productivity may be lowered.
Further, for example, a container having a shape given by processing is usually carried by stacking a large number of containers, and then the containers are taken out one by one, and then the articles are stored in the container. However, if the resin material is not sufficiently slippery or is blocked, a plurality of containers may be taken out while overlapping.

In order to solve such a problem, attempts have been made to improve the surface characteristics so that the surface of the polyester sheet and the surface of the molded product become slippery, and the following techniques are known.
Patent Document 1 describes a non-stretched composition comprising 0.04 to 1% by weight of lubricant particles (silica or the like) having an average particle size of 8 to 50 microns and 99.0 to 99.96% by weight of polyester. Alternatively, a low magnification stretched polyester sheet is disclosed. Patent Document 2 contains internal particles containing calcium element and phosphorus element and silica particles of 50 to 750 ppm, the calcium element content is 0.01 to 0.1% by weight, and the phosphorus element content is Biaxial, which is composed of polyester having an element amount ratio of 0.5 to 2 times the elemental amount ratio to calcium element, and has protrusions having a maximum diameter of 5 μm or less present on the film surface at a density of 20 to 60 pieces / μm ² . Stretched polyester films are disclosed. Further, Patent Document 3 has a laminated structure of at least three layers, and the surface roughness (Ra) of one of the film surfaces is in the range of 0.001 to 0.005 μm, and the layer constituting the surface. It contains 1000 ppm or more of aluminum oxide particles, a release layer and a green sheet are sequentially provided on the surface, and the surface roughness (Ra) of the other film surface is within the range of 0.010 to 0.030 μm. It is a release laminated polyester film for green sheets, and has one or less dents with a depth of 0.2 μm or more on the surface of the green sheet / 100 cm ² , and carbon-carbon double in the layer constituting the surface. Disclosed is a release laminated polyester film for a green sheet, which is a laminated polyester film containing polystyrene particles having a crosslinked structure achieved by a compound containing two or more bonds in one molecule.

Japanese Unexamined Patent Publication No. 5-17598 Japanese Unexamined Patent Publication No. 6-313095 Japanese Unexamined Patent Publication No. 2016-187963

An object of the present invention is a modifier that, in combination with a polyester resin, provides a resin sheet having excellent surface slipperiness without impairing transparency, and a polyester resin composition, polyester resin sheet, laminated sheet containing the same. , Also, to provide a method for manufacturing a molded product.

The present inventors obtained a modifier containing a specific fatty acid ester and having a calcium element content of 0.1 to 3.0% by mass with respect to the modifier in combination with a polyester resin. It has been found that when the obtained resin composition is used, a resin sheet having excellent surface slipperiness can be obtained without impairing the transparency.

The present invention is shown below.
The modifier for a resin sheet of the present invention is a modifier used in the production of a resin sheet, and as a component (A), a polyhydric alcohol having a valence of 3 to 6 and a hydrocarbon having 8 to 22 carbon atoms are carbonized. It contains an ester compound with a fatty acid having a hydrogen group and a compound containing a calcium element as a component (B), and the content ratio of the calcium element is 0.1 to 3.0% by mass with respect to the modifier. It is characterized by being.
The component (B) preferably contains at least one selected from talc and zeolite.
The polyester resin composition of the present invention is a resin composition used for producing a polyester resin sheet, and is characterized by containing a polyester resin and the above-mentioned modifier for a resin sheet of the present invention.
The polyester resin sheet of the present invention is characterized by containing the polyester resin and the above-mentioned modifier for the resin sheet of the present invention.
The laminated sheet of the present invention is characterized by comprising a resin layer made of the polyester resin sheet of the present invention and another resin layer.
The method for producing a molded body of the present invention is characterized in that the polyester resin sheet or laminated sheet of the present invention is subjected to a molding process.

In the present invention, when a polyester resin composition is prepared by using a modifier for a resin sheet in combination with a polyester resin, the polyester resin composition is used to produce a polyester resin sheet having excellent transparency and surface slipperiness. It can be a suitable molding material. The polyester resin composition may be used as it is for producing a polyester resin sheet, or may have a structure (masterbatch) in which the content ratio of the modifier for the resin sheet to the polyester resin is high (masterbatch). A polyester resin sheet can be efficiently manufactured by using a masterbatch and a polyester resin in combination. Further, since the laminated sheet of the present invention includes a resin layer made of a polyester resin sheet having excellent transparency and surface slipperiness, it is at least excellent in slipperiness on the surface of the resin layer.
By subjecting the polyester resin sheet or laminated sheet of the present invention to a conventionally known molding process, a molded product having a predetermined shape can be easily obtained. When a plurality of the obtained molded products are stacked, the occurrence of blocking can be suppressed.

The modifier for a resin sheet of the present invention is a modifier used in the production of a resin sheet, and is a polyhydric alcohol having a component (A) of 3 to 6 and a hydrocarbon group having 8 to 22 carbon atoms. Contains an ester compound with a fatty acid having a component (B) and a compound containing the element (B) calcium.

The component (A) is an ester compound of a polyhydric alcohol and a fatty acid, and is preferably an organic compound composed of a carbon atom, a hydrogen atom, and an oxygen atom and containing an ester bond.

The polyhydric alcohol used to form the component (A) is a compound having 3 to 6 hydroxy groups.

Examples of the polyhydric alcohol include trimethylolethane, trimethylolpropane, glycerin, diglycerin, triglycerin, tetraglycerin, trimethylolethane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, hexanetriol, sorbitan, sorbitol, and erythritol. Examples thereof include mannitol, galactitol, iditol, taritol, and alitol. Of these, glycerin and pentaerythritol are preferred.

The fatty acid used for forming the component (A) is a compound having a carboxy group having an alkyl group having 8 to 22 carbon atoms. In order to make the component (A) of the above preferred embodiment, this fatty acid is an aliphatic compound which may contain a carbon-carbon unsaturated bond, that is, one in an aliphatic saturated hydrocarbon or an unsaturated hydrocarbon. It is a compound in which the hydrogen atom of is substituted with a carboxy group.

Examples of the fatty acids include octanoic acid, decanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, 9-hexadecylic acid, heptadecanoic acid, octadecanoic acid, cis-9-octadecenoic acid, 11-octadecenoic acid and eikosan. Acids, docosanoic acid and the like can be mentioned. Of these, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid and octadecanoic acid, which are saturated fatty acids having an alkyl group having 12 to 18 carbon atoms, are preferable.

The above component (A) is an esterified product of the above polyhydric alcohol and a fatty acid, and the component (A) contained in the modifier for a resin sheet of the present invention may be only one kind, but two or more kinds. May be.

The modifier for a resin sheet of the present invention contains a calcium element. The content ratio (content) of the calcium element in the modifier for the resin sheet is 0.1 to 3.0% by mass, preferably 0, when the total amount of the modifier for the resin sheet is 100% by mass. .3 to 3.0% by mass, particularly preferably 0.5 to 2.0% by mass.
The calcium element contained in the modifier for the resin sheet may be a calcium element derived from the compound having the calcium element of the above component (B), or may be another calcium element. In the present invention, if the content ratio of the calcium element in the modifier for the resin sheet is within the above range, the polyester resin composition can be used in combination with the polyester resin to make the surface slippery without impairing the transparency. A molded body such as an excellent resin sheet can be easily manufactured.

As a method for quantifying the content of calcium element in the modifier for a resin sheet of the present invention, a usual measuring method can be applied. For example, a fluorescent X-ray analysis method and the like can be mentioned.

In the modifier for a resin sheet of the present invention, the compound containing the calcium element of the above component (B) is not particularly limited, and may be either an inorganic compound or an organic compound. Of these, inorganic compounds are preferred, and known talc or zeolites are preferred. The component (B) contained in the modifier for a resin sheet of the present invention may be either one or both of these.

In the case of talc, the component (B) is preferably in the form of particles, and the average particle size obtained by the laser / diffraction scattering method is such that a resin sheet having excellent surface slipperiness can be obtained without impairing transparency. It is preferably 0.5 to 20 μm, and in the case of zeolite, it is 1 to 10 μm.

In the modifier for a resin sheet of the present invention, the content ratios of the above components (A) and (B) are preferably 40 to 80% by mass, respectively, when the total content of these components is 100% by mass. And 20 to 60% by mass.

The modifier for a resin sheet of the present invention may contain other components, if necessary, as long as the transparency of the resin molded body can be obtained. For example, the filler excluding the above component (B) ( Hereinafter, it may contain a plasticizer, an antioxidant, an ultraviolet absorber, a weather resistant agent, a heat stabilizer, an antioxidant, a lubricant, a flame retardant, a crystal nucleating agent and the like.

Other fillers include silica, talc (but not containing calcium element), diatomaceous soil, titanium oxide, alumina, zirconia, zinc oxide, strontium oxide, strontium carbonate, iron oxide, ferrite, zeolite, pyrophyllite, smectite. , Vermiculite, wollastonite, mica, clay and the like. The other filler contained in the modifier for the resin sheet of the present invention may be only one kind or two or more kinds.

The preferred configuration of the modifier for a resin sheet of the present invention is as follows.
(1) Modifier composed of component (A) and component (B) (2) Modifier composed of component (A), component (B) and other fillers

The modifier for a resin sheet of the present invention preferably mixes the component (A), the component (B), and other components used in combination as necessary, using a conventionally known mixing device. Thereby, it can be manufactured.

The modifier for a resin sheet of the present invention contains the above component (A) and the above component (B), and is a resin composition that gives a molded body such as a polyester resin sheet that is transparent and has a smooth surface. Suitable as a manufacturing raw material.

The polyester resin composition of the present invention is used for producing a polyester resin sheet, and contains a polyester resin and a modifier for a resin sheet of the present invention. In the resin composition of the present invention, the amount of the modifier for the resin sheet of the present invention is not limited, but when the content of the polyester resin is 100 parts by mass, the modifier of the present invention is preferably used. It is contained in a proportion of 0.1 to 45 parts by mass. When the content of the polyester resin is 100 parts by mass, the polyester resin composition of the present invention containing the modifier for a resin sheet of the present invention in a ratio of 10 to 45 parts by mass can be used as a masterbatch. ..

The modifier for the resin sheet and the polyester resin contained in the polyester resin composition of the present invention may be only one kind or two or more kinds.

The polyester resin is a thermoplastic resin, and may be either an aromatic polyester resin or an aliphatic polyester resin, or a combination of both. Further, these polyester resins may be either homopolyester or copolyester.

The polyester resin is usually a resin obtained by polycondensation of a dicarboxylic acid component with a dihydroxy component, polycondensation of a dicarboxylic acid component with a dihydroxy component and an oxycarboxylic acid component, ring-opening polymerization of a lactone component, or the like. be.

Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid (2,6-naphthalenedicarboxylic acid, etc.), diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylmethanedicarboxylic acid, diphenylethanedicarboxylic acid, and diphenylketonedicarboxylic acid. Aromatic dicarboxylic acid having 8 to 16 carbon atoms such as acid or a derivative thereof, cyclohexanedicarboxylic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, hymic acid and the like have about 8 to 12 carbon atoms. Adicyclic dicarboxylic acid having 2 to 40 carbon atoms such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecandicarboxylic acid, hexadecanedicarboxylic acid, dimeric acid and the like. Or a derivative thereof and the like.

The dihydroxy component may be linear or linear such as ethylene glycol, trimethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, hexanediol, octanediol, and decanediol. Alicyclic alkylene diols such as branched alkylene diols having 2 to 12 carbon atoms, cyclohexane diols, alicyclic diols such as cyclohexanedimethanol and hydride bisphenol A, hydroquinone, resorcin, dihydroxyphenyl, naphthalene diol and dihydroxy. Aromatic diols such as adducts (diethoxylated bisphenol A, etc.) to which alkylene oxides such as ethylene oxide and propylene oxide are added to diphenyl ether and bisphenol A, diethylene glycol, triethylene glycol, polyethylene glycol, ditetramethylene glycol, and dipropylene. Examples thereof include polyalkylene glycols such as glycols, tripropylene glycols and polypropylene glycols.

Examples of the oxycarboxylic acid component include lactic acid, glycolic acid, 2-hydroxy-n-fatty acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 2-hydroxycaproic acid, and 2-hydroxyisocaproic acid. Examples include oxycarboxylic acids such as 6-hydroxycaproic acid, 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, oxybenzoic acid, oxynaphthoic acid, diphenyleneoxycarboxylic acid and derivatives thereof. Be done.

Examples of the lactone component include ε-propiolactone, δ-butyrolactone, β-butyrolactone, γ-butyrolactone, pivalolactone, δ-valerolactone, and ε-caprolactone.

When the polyester resin is an aromatic homopolyester, it is preferably a polycondensate of a dicarboxylic acid component and a dihydroxy component.
The dicarboxylic acid component is preferably terephthalic acid, naphthalenedicarboxylic acid or the like, and the dihydroxy component is preferably ethylene glycol, diethylene glycol, butanediol, cyclohexanedimethanol or the like. Typical homopolyesters are polyalkylene terephthalates such as polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), polyhexamethylene terephthalate, polycyclohexane-1,4-dimethylterephthalate, and polyneopentyl terephthalate. , Polyalkylene naphthalate such as polyethylene isophthalate, polyethylene naphthalate, polybutylene naphthalate, polyhexamethylene naphthalate and the like. Of these, PET is particularly preferable.

When the polyester resin is an aromatic copolyester, it is preferably a polycondensate of a dicarboxylic acid component, a dihydroxy component, and an oxycarboxylic acid component.
The dicarboxylic acid component is preferably one or more selected from isophthalic acid, phthalic acid, terephthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid and the like, and the dihydroxy component is preferably ethylene glycol. One or more of diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, neopentylglycol and the like, and the oxycarboxylic acid is, for example, p-oxybenzoic acid and the like. Typical copolyester resins are condensates of terephthalic acid, ethylene glycol and 4-cyclohexanedimethanol (sometimes referred to as "PETG resin"), polyethylene terephthalate / isophthalate resins and the like.

When the above polyester resin is an aliphatic polyester resin, a ring-opening polymerization reaction of a cyclic lactone, a polycondensation reaction of an aliphatic hydroxycarboxylic acid (oxycarboxylic acid), an aliphatic dibasic acid (succinic acid, adipic acid, azelaic acid, etc.) Sevacinic acid, α, ω-dodecandicarboxylic acid, dodecenylsuccinic acid, octadecenyldicarboxylic acid, cyclohexanedicarboxylic acid, etc.) and / or ester-forming compounds thereof (dimethyl succinate, dimethyl adipate, dimethyl azelaite, dimethyl sebacate) Aliphatic compounds having two or more ester bond-forming functional groups in the molecule, such as, and aliphatic diols (ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butane). It is preferably a resin obtained by a polycondensation reaction with a diol (diol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, cyclohexanedimethanol, etc.).

Examples of the aliphatic polyester resin obtained by the ring-opening polymerization reaction of the cyclic lactone include poly (ε-propiolactone) resin, poly (δ-butyrolactone) resin, poly (β-butyrolactone) resin, and poly (γ-butyrolactone). Examples thereof include a resin, a poly (pivalolactone) resin, a poly (δ-valerolactone) resin, and a poly (ε-caprolactone) resin.

Examples of the aliphatic polyester resin obtained by the polycondensation reaction of the aliphatic hydroxycarboxylic acid (oxycarboxylic acid) include polylactic acid resin, polyglycolic acid resin, poly (3-hydroxybutyric acid) resin, and poly (4-hydroxybutyric acid). Examples thereof include resins and poly (4-hydroxyvaleric acid) resins.

The polyester resin preferably contains an aromatic polyester resin.

The polyester resin composition of the present invention may contain other components, if necessary, as long as the transparency of the resin sheet can be obtained. For example, a filler excluding the component (B), a plasticizer, and oxidation. It can contain an inhibitor, an ultraviolet absorber, a weather resistant agent, a heat stabilizer, an antistatic agent, a lubricant, a flame retardant, a crystal nucleating agent and the like.

When the polyester resin composition of the present invention is a masterbatch, it can have, for example, a columnar shape, a prismatic shape, a spherical shape, an elliptical spherical shape, or the like.

The masterbatch is produced by heating a mixture containing the modifier for a resin sheet of the present invention and a polyester resin to form a melt-kneaded product, and then subjecting the mixture to a conventionally known extrusion method. be able to. The specific manufacturing method is shown below.
(1) The above-mentioned modifier for a resin sheet of the present invention and a polyester resin are put into a mixer such as a tumbler blender, a henschel mixer, or a super mixer and mixed, and then a single-screw extruder, a multi-screw extruder, or the like. Method of obtaining a masterbatch by granulating while melt-kneading with the extruder (2) The resin sheet of the present invention is placed in a molten state by an extruder such as a single-screw extruder or a multi-screw extruder. A method of mixing plastic modifiers, additives, etc. by side feeding or liquid injection, and granulating while melt-kneading to obtain a masterbatch.

The polyester resin sheet of the present invention contains the above-mentioned modifier for the resin sheet of the present invention. The modifier for a resin sheet in a polyester resin sheet which is transparent and has a smooth surface is contained in a preferable ratio. That is, the modifier for a resin sheet is preferably contained in a proportion of 0.1 to 1.5 parts by mass when the content of the polyester resin is 100 parts by mass. The component (A) is contained in a proportion of 0.02 to 1.2 parts by mass, preferably 0.04 to 1.2 parts by mass. The calcium element is contained in a proportion of 0.0001 to 0.045 parts by mass, preferably 0.0003 to 0.045 parts by mass, and more preferably 0.0005 to 0.03 parts by mass.

The thickness of the polyester resin sheet of the present invention is not particularly limited, but is preferably 100 to 800 μm, more preferably 300 to 500 μm.

The polyester resin sheet of the present invention is transparent, and when subjected to HAZE measurement by a method according to JIS K 7136, the HAZE is preferably 10% or less, more preferably 5% or less. Therefore, the visibility of the article on the opposite side is excellent through this resin sheet.

Further, when the polyester resin sheet of the present invention is subjected to the static friction coefficient measurement of the method according to JIS K 7125, the static friction coefficient is preferably 0.40 or less, more preferably 0.35 or less. Since the polyester resin sheet of the present invention has the above-mentioned properties, its surface is smooth, and when a plurality of resin sheets are overlapped with each other, they can be easily taken out one by one without causing blocking.

The polyester resin sheet of the present invention can be produced by subjecting the polyester resin composition of the present invention to conventionally known molding means such as calendar molding, T-die molding, inflation molding, blow molding and the like. If necessary, the stretching process can be performed. After that, by subjecting the polyester resin sheet of the present invention to secondary processing such as vacuum forming, pressure forming, punching, and assembling, a molded body having a predetermined shape such as a container can be manufactured.

Further, the polyester resin sheet of the present invention can be used to manufacture a resin sheet having a multi-layer structure, that is, a laminated sheet. In the present invention, it is a laminated sheet composed of a polyester resin sheet having a resin structure that is transparent and has a smooth surface thereof and another resin layer. For example, both the surface layers on the one surface side and the surface layer on the other surface side are , The polyester resin sheet of the present invention may be used, and the intermediate layer may be a three-layer laminated sheet having another resin composition. In the laminated sheet of such an embodiment, when the HAZE is preferably 10% or less, more preferably 5% or less, the visibility of the article on the opposite side through the sheet is excellent. The laminated sheet of the present invention is not limited to the three-layer type laminated sheet, and may be a two-layer type laminated sheet or a laminated sheet composed of four or more layers.

The three-layer laminated sheet can be manufactured by a coextrusion method, a laminating method, or the like. Of these, in the case of the coextrusion method, a molding material (heat) containing the polyester resin forming the surface layer on one surface side and the surface layer on the other surface side and the modifier for the resin sheet of the present invention. A method of subjecting the plastic resin composition) and the molding material (thermoplastic resin composition) for forming the intermediate layer to inflation molding or T-die molding can be used, and if necessary, the molding material is stretched. You can also. Moreover, as a laminating method, a dry laminating method, a sand laminating method, an extrusion laminating method and the like can be mentioned. When manufactured by these laminating methods, it contains a polyester resin for forming a surface layer on one side and a surface layer on the other side, and the above-mentioned modifier for a resin sheet of the present invention. It can be laminated with an adhesive interposed between the polyester resin sheet and the resin film for forming the intermediate layer.

By subjecting the laminated sheet of the present invention to secondary processing such as vacuum forming, pressure forming, punching, and assembling, as in the case of the polyester resin sheet of the present invention, a molded body having a predetermined shape such as a container is obtained. Can be manufactured.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. Here, parts and% are based on mass unless otherwise specified.

1. 1. Raw materials for resin sheet modifiers and quantification of calcium elements The raw materials used to manufacture resin sheet modifiers are shown below. The average particle size of the filler is a measured value by a laser diffraction / scattering method.

(1) Fatty acid ester A-1: Pentaerythritol tetrastearate A-2: Glycerin tristearate A-3: Sorbitane tristearate A-4: Glycerin monostearate A-5: Diglycerin monolaurate A-6 : Pentaerythritol distearate a-1: Ethylene glycol monostearate a-2: Decaglycerin monolaurate

(2) Filler (compound containing calcium element)
B-1: Zeolite particles (average particle size: 7 μm, Ca amount: 5.73%)
B-2: Zeolite particles (average particle size: 5 μm, Ca amount: 5.20%)
B-3: Zeolite particles (average particle size: 3 μm, Ca amount: 5.26%)
B-4: Zeolite particles (average particle size: 10 μm, Ca amount: 5.40%)
B-5: Talc particles (average particle size: 4 μm, Ca amount: 0.19%)
B-6: Talc particles (average particle size: 6 μm, Ca amount: 0.29%)
B-7: Talc particles (average particle size: 10 μm, Ca amount: 0.10%)
B-8: Talc particles (average particle size: 15 μm, Ca amount: 0.27%)
B-9: Zeolite particles (average particle size: 12 μm, Ca amount: 5.54%)
B-10: Zeolite particles (average particle size: 0.5 μm, Ca amount: 5.20%)

(3) Other filler C-1: Silica particles (average particle size: 3 μm)
C-2: Talc particles (average particle size: 8 μm, Ca-free)
C-3: Silica particles (average particle size: 8 μm)
C-4: Silica particles (average particle size: 3 μm)
C-5: Silica particles (average particle size: 0.5 μm)

(4) Quantification of Calcium Element The content ratio (content) of calcium element in the modifier for resin sheets in Examples and Comparative Examples was quantified by a fluorescent X-ray analyzer "ZSX101e" manufactured by Rigaku Corporation.

2. 2. Production of modifier for resin sheet Example 1-1
38.5 parts of fatty acid ester A-1, 7.7 parts of zeolite particles B-1, 30.8 parts of talc particles B-5, 7.7 parts of silica particles C-1 and 15. Three parts of talc particles C-2 were stirred with a mixer to obtain a resin sheet modifier (hereinafter referred to as "resin sheet modifier E-1") composed of a uniform mixture (see Table 1). .. In Table 1, the ratio when the total of the components (A) and (B) according to the present invention is 100% and the ratio (Ca amount) of the calcium element contained in the modifier for the resin sheet are also shown. did.

Example 1-2
Using 50 parts of fatty acid ester A-1, 15 parts of zeolite particles B-1, and 35 parts of talc particles C-2, the same operation as in Example 1-1 was performed to modify the resin sheet. (Hereinafter referred to as "modified agent E-2 for resin sheet") was obtained (see Table 1).

Example 1-3
Performed using 60 parts of fatty acid ester A-1, 2.5 parts of fatty acid ester A-4, 9.4 parts of zeolite particles B-1, and 28.1 parts of zeolite particles B-2. The same operation as in Example 1-1 was carried out to obtain a modifier for a resin sheet (hereinafter referred to as “modified agent E-3 for a resin sheet”) (see Table 1).

Example 1-4
Using 60 parts of fatty acid ester A-2, 25 parts of zeolite particles B-2, and 15 parts of silica particles C-3, the same operation as in Example 1-1 was performed to modify the resin sheet. (Hereinafter referred to as “resin sheet modifier E-4”) was obtained (see Table 1).

Example 1-5
Using 40 parts of fatty acid ester A-2, 30 parts of zeolite particles B-4, and 30 parts of talc particles B-7, the same operation as in Example 1-1 was performed to modify the resin sheet. (Hereinafter referred to as "modified agent E-5 for resin sheet") was obtained (see Table 1).

Example 1-6
Using 59 parts of the fatty acid ester A-1, 6.3 parts of the zeolite particles B-3, and 34.7 parts of the talc particles B-6, the same operation as in Example 1-1 was performed to perform the same operation as in Example 1-1. A modifier for resin sheet (hereinafter referred to as “modified agent for resin sheet E-6”) was obtained (see Table 1).

Example 1-7
Using 40.5 parts of fatty acid ester A-1, 46.5 parts of zeolite particles B-3, and 13 parts of talc particles B-8, the same operation as in Example 1-1 was carried out to perform the same operation as in Example 1-1. A modifier for resin sheet (hereinafter referred to as “modified agent for resin sheet E-7”) was obtained (see Table 1).

Example 1-8
Using 27.3 parts of fatty acid ester A-2, 31.8 parts of zeolite particles B-3, and 40.9 parts of talc particles B-5, the same operation as in Example 1-1 was performed. A resin sheet modifier (hereinafter referred to as “resin sheet modifier E-8”) was obtained (see Table 1).

Example 1-9
Using 70 parts of fatty acid ester A-2, 3.7 parts of fatty acid ester A-5, and 26.3 parts of zeolite particles B-9, the same operation as in Example 1-1 was carried out to perform the same operation as in Example 1-1. A modifier for resin sheet (hereinafter referred to as “modified agent for resin sheet E-9”) was obtained (see Table 1).

Example 1-10
Using 78.6 parts of fatty acid ester A-2, 1.4 parts of zeolite particles B-1, and 20 parts of talc particles B-5, the same operation as in Example 1-1 was carried out to perform the same operation as in Example 1-1. A modifier for resin sheet (hereinafter referred to as “modified agent for resin sheet E-10”) was obtained (see Table 1).

Example 1-11
Using 61.1 parts of fatty acid ester A-3 and 38.9 parts of zeolite particles B-10, the same operation as in Example 1-1 was carried out to perform a modifier for a resin sheet (hereinafter, “resin sheet”). (Refer to Table 1).

Comparative Example 1-1
Using 47.4 parts of fatty acid ester A-1, 1.4 parts of zeolite particles B-1, and 51.2 parts of silica particles C-4, the same operation as in Example 1-1 was performed. A resin sheet modifier (hereinafter referred to as “resin sheet modifier e-1”) was obtained (see Table 1).

Comparative Example 1-2
Using 25 parts of the fatty acid ester A-6 and 75 parts of the zeolite particles B-10, the same operation as in Example 1-1 was carried out to perform a resin sheet modifier (hereinafter, “resin sheet modifier”). e-2 ”) was obtained (see Table 1).

Comparative Example 1-3
Using 62.5 parts of fatty acid ester a-1, 18.75 parts of zeolite particles B-1, and 18.75 parts of silica particles C-3, the same operation as in Example 1-1 was performed. A resin sheet modifier (hereinafter referred to as “resin sheet modifier e-3”) was obtained (see Table 1).

Comparative Example 1-4
Performed using 30.3 parts of fatty acid ester a-2, 15.15 parts of zeolite particles B-2, 14.55 parts of talc particles C-2, and 40 parts of silica particles C-5. The same operation as in Example 1-1 was carried out to obtain a resin sheet modifier (hereinafter referred to as “resin sheet modifier e-4”) (see Table 1).

3. 3. Production of Masterbatch (Resin Composition) Masterbatch (resin composition) using the above-mentioned modifier for resin sheet and polyethylene terephthalate "BG-80" (trade name) manufactured by Sinopec Yizheng Chemical Fibers Co., Ltd. ) Was manufactured.

Example 2-1
After stirring 100 parts of the above polyethylene terephthalate (PET) and 35.1 parts of the modifier E-1 for a resin sheet with a tumbler, a twin-screw kneading extruder "TEX30α" (model name) manufactured by Japan Steel Works, Ltd. ) Was melt-kneaded at 250 ° C to 270 ° C to obtain a master batch M-1 (see Table 2).

Example 2-2
Using 100 parts of the above polyethylene terephthalate (PET) and 25.0 parts of the modifier E-2 for a resin sheet, the same operation as in Example 2-1 was carried out to obtain a masterbatch M-2. (See Table 2).

Example 2-3
Using 100 parts of the above polyethylene terephthalate (PET) and 25.0 parts of the modifier E-4 for a resin sheet, the same operation as in Example 2-1 was carried out to obtain a masterbatch M-3. (See Table 2).

Example 2-4
Using 100 parts of the above polyethylene terephthalate (PET) and 25.0 parts of the modifier E-5 for a resin sheet, the same operation as in Example 2-1 was carried out to obtain a masterbatch M-4. (See Table 2).

Example 2-5
Using 100 parts of the above polyethylene terephthalate (PET) and 22.7 parts of the modifier E-7 for a resin sheet, the same operation as in Example 2-1 was carried out to obtain a masterbatch M-5. (See Table 2).

Example 2-6
Using 100 parts of the above polyethylene terephthalate (PET) and 22.0 parts of the modifier E-11 for a resin sheet, the same operation as in Example 2-1 was carried out to obtain a masterbatch M-6. (See Table 2).

4. Production of Resin Composition, Production of Resin Sheet, and Evaluation thereof Using the above-mentioned polyethylene terephthalate (PET) and the above-mentioned modifier for resin sheet or masterbatch, a resin composition for forming a resin sheet is produced. did.

Example 3-1
After stirring 100 parts of the above polyethylene terephthalate (PET) and 0.50 parts of the modifier E-1 for a resin sheet with a tumbler, a twin-screw kneading extruder "TEX30α" (model name) manufactured by Japan Steel Works, Ltd. ) Was melt-kneaded at 250 ° C to 270 ° C to obtain a composition for producing a resin sheet (hereinafter referred to as “resin composition T-1”). Next, the melt-kneaded product of this resin composition T-1 was extruded from a T-die onto a cooling roll whose temperature was adjusted to 40 ° C. to obtain a resin sheet having a thickness of 300 μm (hereinafter referred to as “resin sheet S-1”). (See Table 3).

The obtained resin sheet S-1 was evaluated for slipperiness and transparency by the following method, and the results are also shown in Table 3.

(1) The slippery resin sheet was subjected to 20 ° C. and 65% R. H. After adjusting the humidity for 24 hours, the static friction coefficient was measured in the same atmosphere using a friction measuring machine "TR-2" (model name) manufactured by Toyo Seiki Co., Ltd. in accordance with JIS K7125. The measurement was performed on an arbitrary surface of three resin sheets, and the average value of a total of three points was adopted to evaluate the slipperiness according to the following criteria.
◎ ◎: 0.35 or less ◎: More than 0.35 to 0.40 or less 〇: More than 0.40 to 0.60 or less ×: More than 0.60

(2) The HAZE of the transparent resin sheet was measured using a haze meter "NDH5000" (model name) manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with JIS K7136. The measurement was performed on an arbitrary position of 5 resin sheets, and the average value of a total of 5 points was adopted to evaluate the transparency according to the following criteria.
◎: 5% or less 〇: Over 5% to 10% or less ×: Over 10%

Example 3-2
The resin composition T-2 was produced in the same manner as in Example 3-1 except that 99.60 parts of the above polyethylene terephthalate (PET) and 0.54 parts of the masterbatch M-1 were used. , The resin sheet S-2 shown in Table 3 was manufactured. Then, slipperiness and transparency were evaluated (see Table 3).

Example 3-3
The resin composition T-3 was produced in the same manner as in Example 3-1 except that 96.58 parts of the above polyethylene terephthalate (PET) and 4.62 parts of the masterbatch M-1 were used. , The resin sheet S-3 shown in Table 3 was manufactured. Then, slipperiness and transparency were evaluated (see Table 3).

Example 3-4
A resin composition T-4 was produced in the same manner as in Example 3-1 except that 100 parts of the above polyethylene terephthalate (PET) and 1.01 part of the modifier E-1 for a resin sheet were used. Then, the resin sheet S-4 shown in Table 3 was manufactured. Then, slipperiness and transparency were evaluated (see Table 3).

Example 3-5
A resin composition T-5 was produced in the same manner as in Example 3-1 except that 100 parts of the above polyethylene terephthalate (PET) and 0.60 parts of the modifier E-2 for a resin sheet were used. Then, the resin sheet S-5 shown in Table 3 was manufactured. Then, slipperiness and transparency were evaluated (see Table 3).

Example 3-6
The resin composition T-6 was produced in the same manner as in Example 3-1 except that 98.48 parts of the above polyethylene terephthalate (PET) and 1.90 parts of the masterbatch M-2 were used. , The resin sheet S-6 shown in Table 3 was manufactured. Then, slipperiness and transparency were evaluated (see Table 3).

Example 3-7
A resin composition T-7 was produced in the same manner as in Example 3-1 except that 100 parts of the above polyethylene terephthalate (PET) and 0.91 part of the modifier E-3 for a resin sheet were used. Then, the resin sheet S-7 shown in Table 3 was manufactured. Then, slipperiness and transparency were evaluated (see Table 3).

Example 3-8
A resin composition T-8 was produced in the same manner as in Example 3-1 except that 100 parts of the above polyethylene terephthalate (PET) and 0.55 parts of the modifier E-4 for a resin sheet were used. Then, the resin sheet S-8 shown in Table 3 was manufactured. Then, slipperiness and transparency were evaluated (see Table 3).

Example 3-9
The resin composition T-9 was produced in the same manner as in Example 3-1 except that 95.60 parts of the above polyethylene terephthalate (PET) and 5.50 parts of the masterbatch M-3 were used, and then the resin composition T-9 was produced. , The resin sheet S-9 shown in Table 3 was manufactured. Then, slipperiness and transparency were evaluated (see Table 3).

Example 3-10
A resin composition T-10 was produced in the same manner as in Example 3-1 except that 100 parts of the above polyethylene terephthalate (PET) and 0.70 parts of the modifier E-5 for a resin sheet were used. Then, the resin sheet S-10 shown in Table 3 was manufactured. Then, slipperiness and transparency were evaluated (see Table 3).

Example 3-11
The resin composition T-11 was produced in the same manner as in Example 3-1 except that 97.20 parts of the above polyethylene terephthalate (PET) and 3.50 parts of the masterbatch M-4 were used. , The resin sheet S-11 shown in Table 3 was manufactured. Then, slipperiness and transparency were evaluated (see Table 3).

Example 3-12
A resin composition T-12 was produced in the same manner as in Example 3-1 except that 100 parts of the above polyethylene terephthalate (PET) and 0.81 part of the modifier E-6 for a resin sheet were used. Then, the resin sheet S-12 shown in Table 3 was manufactured. Then, slipperiness and transparency were evaluated (see Table 3).

Example 3-13
A resin composition T-13 was produced in the same manner as in Example 3-1 except that 100 parts of the above polyethylene terephthalate (PET) and 0.50 parts of the modifier E-7 for a resin sheet were used. Then, the resin sheet S-13 shown in Table 3 was manufactured. Then, slipperiness and transparency were evaluated (see Table 3).

Example 3-14
The resin composition T-14 was produced in the same manner as in Example 3-1 except that 93.83 parts of the above polyethylene terephthalate (PET) and 7.57 parts of the masterbatch M-5 were used, and then the resin composition T-14 was produced. , The resin sheet S-14 shown in Table 3 was manufactured. Then, slipperiness and transparency were evaluated (see Table 3).

Example 3-15
A resin composition T-15 was produced in the same manner as in Example 3-1 except that 100 parts of the above polyethylene terephthalate (PET) and 0.20 parts of the modifier E-8 for a resin sheet were used. Then, the resin sheet S-15 shown in Table 3 was manufactured. Then, slipperiness and transparency were evaluated (see Table 3).

Example 3-16
A resin composition T-16 was produced in the same manner as in Example 3-1 except that 100 parts of the above polyethylene terephthalate (PET) and 1.32 parts of the modifier E-9 for a resin sheet were used. Then, the resin sheet S-16 shown in Table 3 was manufactured. Then, slipperiness and transparency were evaluated (see Table 3).

Example 3-17
A resin composition T-17 was produced in the same manner as in Example 3-1 except that 100 parts of the above polyethylene terephthalate (PET) and 1.21 parts of the modifier E-10 for a resin sheet were used. Then, the resin sheet S-17 shown in Table 3 was manufactured. Then, slipperiness and transparency were evaluated (see Table 3).

Example 3-18
A resin composition T-18 was produced in the same manner as in Example 3-1 except that 100 parts of the above polyethylene terephthalate (PET) and 1.01 parts of the modifier E-11 for a resin sheet were used. Then, the resin sheet S-18 shown in Table 3 was manufactured. Then, slipperiness and transparency were evaluated (see Table 3).

Example 3-19
The resin composition T-19 was produced in the same manner as in Example 3-1 except that 98.18 parts of the above polyethylene terephthalate (PET) and 2.22 parts of the masterbatch M-6 were used. , The resin sheet S-19 shown in Table 3 was manufactured. Then, slipperiness and transparency were evaluated (see Table 3).

Comparative Example 3-1
A resin composition t-1 was produced in the same manner as in Example 3-1 except that 100 parts of the above polyethylene terephthalate (PET) and 0.50 parts of the modifier e-1 for a resin sheet were used. Then, the resin sheet s-1 shown in Table 3 was manufactured. Then, slipperiness and transparency were evaluated (see Table 3).

Comparative Example 3-2
A resin composition t-2 was produced in the same manner as in Example 3-1 except that 100 parts of the above polyethylene terephthalate (PET) and 0.30 parts of the modifier e-2 for a resin sheet were used. Then, the resin sheet s-2 shown in Table 3 was manufactured. Then, slipperiness and transparency were evaluated (see Table 3).

Comparative Example 3-3
A resin composition t-3 was produced in the same manner as in Example 3-1 except that 100 parts of the above polyethylene terephthalate (PET) and 0.81 part of the modifier e-3 for a resin sheet were used. Then, the resin sheet s-3 shown in Table 3 was manufactured. Then, slipperiness and transparency were evaluated (see Table 3).

Comparative Example 3-4
A resin composition t-4 was produced in the same manner as in Example 3-1 except that 100 parts of the above polyethylene terephthalate (PET) and 0.50 parts of the modifier e-4 for a resin sheet were used. Then, the resin sheet s-4 shown in Table 3 was manufactured. Then, slipperiness and transparency were evaluated (see Table 3).

As is clear from the results in Table 3, in Examples 3-1 to 3-19, since the resin composition containing the modifier for the resin sheet according to the present invention was used, it was excellent while maintaining high transparency. It can be seen that a slippery sheet was obtained. Further, in Examples 3-2, 3-3, 3-6, 3-9, 3-11, 3-14 and 3-19, an example in which a polyester resin sheet was produced using the master batch shown in Table 2. Therefore, when the content of the polyester resin is 100 parts by mass, a polyester resin sheet can be suitably produced by using a masterbatch composed of a resin composition containing 10 to 45 parts by mass of a modifier for a resin sheet. It turns out that it is possible.

5. Manufacture of Laminated Sheet and Evaluation thereof A laminated sheet was manufactured using the polyester resin composition obtained above and polyethylene terephthalate "BG-80" (trade name) manufactured by Sinopec Yizheng Chemical Fibers Co., Ltd. of China.

Example 4-1
The resin composition T-1 for producing the resin sheet S-1 produced in the same manner as in Example 3-1 was placed on both surface layers, the polyethylene terephthalate resin was used as an intermediate layer, and each melt-kneaded product was placed at 40 ° C. from the T-die. A three-layer laminated sheet (hereinafter referred to as "laminated sheet U-1") having a thickness of 300 μm and a layer ratio of 1/8/1 was obtained by co-extruding onto a cooling roll whose temperature was adjusted to the above (see Table 4).

The obtained laminated sheet U-1 was evaluated for slipperiness and transparency according to the same evaluation criteria as the resin sheet, and the results are also shown in Table 4.

Examples 4-2 to 4-19
In the same manner as in Example 4-1 using the resin compositions (T-2 to T-19) for producing the polyester resin sheets (S-2 to S-19) shown in Table 3, the laminated sheets shown in Table 4. U-2 to U-19 were obtained (see Table 4).

Comparative Examples 4-1 to 4-4
In the same manner as in Example 4-1 using the resin compositions (t-1 to t-4) for producing the polyester resin sheets (s-1 to s-4) shown in Table 3, the laminated sheet shown in Table 4. u-1 to u-4 were obtained (see Table 4).

As is clear from the results in Table 4, in Examples 4-1 to 4-19, polyethylene terephthalate resin was used as an intermediate layer, and the surface layers (both surface layers) of the intermediate layer were modified for the resin sheet according to the present invention. Since it is a laminated sheet having a three-layer structure using a resin composition containing an agent, it can be seen that it is a laminated sheet having excellent slipperiness while maintaining high transparency.

6. Production of Molded Product and Evaluation thereof A molded product was produced using the above polyester resin sheet or laminated sheet.

Example 5-1
Using the polyester resin sheet (S-1) shown in Table 3, vacuum forming was performed at a resin temperature of 90 ° C. using an NGF-0912 type vacuum forming machine manufactured by Fuse Vacuum Co., Ltd., and the length was 10 cm × width 15 cm × depth 3 cm. (Hereinafter referred to as "molded body V-1") was obtained (see Table 5).

The bottom surface of the tray mold was cut out from the obtained molded product V-1, and the slipperiness and transparency were evaluated according to the same evaluation criteria as the resin sheet, and the results are also shown in Table 5.

Examples 5-2 to 5-19
Molds V-2 to V-19 shown in Table 5 were obtained using the polyester resin sheets (S-2 to S-19) shown in Table 3 in the same manner as in Example 5-1 (see Table 5). ..

Examples 5-20 to 5-38
Molds V-20 to V-38 shown in Table 6 were obtained using the laminated sheets (U-1 to U-19) shown in Table 4 in the same manner as in Example 5-1 (see Table 6).

Comparative Examples 5-1 to 5-4
Molds v-1 to v-4 shown in Table 7 were obtained using the polyester resin sheets (s-1 to s-4) shown in Table 3 in the same manner as in Example 5-1 (see Table 7). ..

Comparative Examples 5-5 to 5-8
Molds v-5 to v-8 shown in Table 7 were obtained using the laminated sheets (u-1 to u-4) shown in Table 4 in the same manner as in Example 5-1 (see Table 7).

As is clear from the results of Tables 5 to 7, Examples 5-1 to 5-38 are obtained from the resin sheet and the laminated sheet using the resin composition containing the modifier for the resin sheet according to the present invention. Since it is a molded product, it can be seen that it is a molded product having excellent slipperiness while maintaining high transparency.

The modifier for a resin sheet and the masterbatch of the present invention are suitable as raw materials for producing a resin composition that has excellent transparency and gives a polyester resin molded product having a smooth surface. Further, the polyester resin molded body obtained by the present invention is suitable for a film, a sheet, a lid, a container, a bag-shaped material for accommodating an article inside, and the like. Since the surface of this molded product is smooth, when the molded products are overlapped with each other, it can be easily taken out one by one or one by one without causing blocking.

Claims (13)

A modifier used in the manufacture of resin sheets.
Modification for resin sheets, which contains the following component (A) and the following component (B), and contains calcium element in the modifier in a proportion of 0.1 to 3.0% by mass. Agent.
Component (A): An ester compound of a 3- to 6-valent polyhydric alcohol and a fatty acid having a hydrocarbon group having 8 to 22 carbon atoms.
Component (B): A compound containing an element of calcium. The modifier for a resin sheet according to claim 1, wherein the polyhydric alcohol used for forming the component (A) contains at least one selected from pentaerythritol and glycerin. The modifier for a resin sheet according to claim 1 or 2, wherein the fatty acid used for forming the component (A) has a hydrocarbon group having 12 to 18 carbon atoms. The modifier for a resin sheet according to any one of claims 1 to 3, wherein the component (B) contains at least one selected from talc and zeolite. When the total content of the component (A) and the component (B) is 100% by mass, the component (A) is 40 to 80% by mass and the component (B) is 20 to 60% by mass. The modifier for a resin sheet according to claim 4, which is contained in 1. A resin composition used in the production of polyester resin sheets.
A polyester resin composition comprising a polyester resin and the modifier for a resin sheet according to any one of claims 1 to 5. The polyester resin composition according to claim 6, wherein when the content ratio of the polyester resin is 100 parts by mass, the modifier for a resin sheet is contained in a ratio of 0.1 to 45 parts by mass. The polyester resin composition according to claim 7, wherein when the content of the polyester resin is 100 parts by mass, the modifier for a resin sheet is contained in a ratio of 10 to 45 parts by mass. A polyester resin sheet comprising the polyester resin and the modifier for the resin sheet according to any one of claims 1 to 5. The polyester resin sheet according to claim 9, wherein the polyester resin content ratio is 100 parts by mass, and the resin sheet modifier is contained in a ratio of 0.1 to 1.5 parts by mass. A laminated sheet comprising the resin layer made of the polyester resin sheet according to claim 9 or 10 and another resin layer. A method for producing a molded product, which comprises subjecting the polyester resin sheet according to claim 9 or 10 to a molding process. A method for manufacturing a molded product, which comprises subjecting the laminated sheet according to claim 11 to a molding process.