JP6871653B1 - Method for manufacturing resin sheet modifiers, surface-modified resin sheets and molded products - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface-modified resin sheet having excellent antifogging property, slipperiness and antistatic property in a modified layer arranged on one surface side, and a modifier for a resin sheet suitable as a material for forming the modified layer. , And a method for manufacturing a molded product. The modifier for a resin sheet of the present invention is characterized by containing (A) an inorganic compound containing an alkali metal element (lithium, sodium or potassium). Further, (B) hydrophilic acrylic resin, (C) lubricant and the like can be contained. [Selection diagram] None

Description

The present invention is a surface-modified resin sheet having excellent antifogging property, slipperiness and antistatic property in the modified layer arranged on one surface side, and a modification for a resin sheet suitable as a material for forming the modified layer. Regarding agents. The present invention also relates to a method for producing a molded product using the surface-modified resin sheet.

Conventionally, thin-walled resin molded products (sheets, containers, etc.) have been widely used for packaging various parts, food products, and other products. When packaging foods, electronic parts, etc., antifogging properties, slipperiness, antistatic properties, etc. may be required, especially on the inner surface side of the above-mentioned molded articles for packaging.
The following techniques are known to impart these performances.

For example, Patent Document 1 describes a vinyl copolymer having a specific structure and a number average molecular weight of 1000 to 100,000, an organic carboxylic acid, and an organic carboxylate in order to impart antifogging and antistatic properties. One or more lubricants selected from organic carboxylic acid esters, organic carboxylic acid amides, polyethylene waxes, silicone oils, silica particles, silicone resin particles and talc powders, 30/70 to 90/10 (weight ratio). A surface treatment agent for a synthetic polymer film, which is characterized by containing the above-mentioned ratio, is disclosed.
Patent Document 2 describes, as an antifogging agent to be applied to a base resin sheet, a partial ester compound of citrus sugar and an aliphatic monocarboxylic acid having 12 to 22 carbon atoms, and an aliphatic monocarboxylic acid having 14 to 22 carbon atoms. Antifogging agents containing acid-alkali metal salts are disclosed.
Further, Patent Document 3 describes an antifogging agent (A) made of a nonionic surfactant or the like, and (T-90) ° C. to (T + 20) ° C. when the heating temperature of the secondary molding is T ° C. A coating liquid for an antifogging layer containing an antifogging aid (B) containing a hydrophilic (meth) acrylic polymer (B1) having a softening point is disclosed. And, this coating liquid can contain a metal compound (D), and it is described that a compound of a polyvalent metal ion (magnesium chloride or the like) is particularly preferable.

Japanese Unexamined Patent Publication No. 2004-244605 Japanese Unexamined Patent Publication No. 2007-031545 JP-A-2018-176740

In recent years, packaging containers and resin sheets for foods, electronic parts, etc. are required to have a higher level of antistatic property in addition to antifogging property and slipperiness.
The problem to be solved by the present invention is as a surface-modified resin sheet having excellent antifogging property, slipperiness and antistatic property in the modified layer arranged on at least one surface side and a material for forming the modified layer thereof. It is to provide a suitable modifier for a resin sheet. Another object is to provide a method for manufacturing a molded product such as a container using such a surface-modified resin sheet. In the present specification, "anti-fog property" means, for example, 5 ° C. in a state where an article containing water or having moisture on the surface is wrapped with a surface-modified resin sheet (with the modified layer on the article side). After being placed in the following atmosphere and left to stand, almost no water droplets that tend to remain on the surface of the modified layer are observed, and the performance is such that the article can be visually recognized well through the sheet.

As a result of diligent research, the present inventors have conducted a layer containing an inorganic compound containing an alkali metal element , a hydrophilic acrylic resin containing a specific structural unit, and a modifier for a resin sheet containing a specific lubricant (modified). It has been found that the surface-modified resin sheet obtained by forming the quality layer) on the surface of the base resin sheet is excellent in antifogging property, slipperiness and antistatic property.
The present invention is shown below.

（式中、Ｒ ^１ は、水素原子又はメチル基であり、Ｒ ^２ は、炭素原子数１〜４の２価の炭化水素基であり、Ｒ ^３ 及びＲ ^４ は、互いに、同一の又は異なる、炭素原子数１〜４の炭化水素基である。）
上記成分（Ｃ）は、炭化水素基の炭素原子数が１４〜２２の脂肪族カルボン酸のナトリウム塩及びカリウム塩から選ばれた少なくとも１つの有機カルボン酸塩であり、
上記成分（Ａ）、上記成分（Ｂ）及び上記成分（Ｃ）の含有割合が、これらの合計を１００質量％とした場合に、それぞれ、０．１〜１５．０質量％、３５．０〜８５．０質量％、及び、１５．０〜６０．０質量％であり、
多価金属イオンを含有しないことを特徴とする。 The modifier for a resin sheet of the present invention is a modifier used for surface modification of a resin sheet (hereinafter referred to as "base resin sheet"), and is an inorganic compound (A) containing an alkali metal element and hydrophilic. acrylic resin (B), and, a lubricant containing (C), the component (a), Ri least 1 Tsudea selected from lithium, halides and sulfates of sodium or potassium, the component (B) Is a polymer containing a structural unit derived from a compound represented by the following formula (1).

(In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a divalent hydrocarbon group having 1 to 4 carbon atoms, and R ³ and R ⁴ are the same or different from each other. It is a hydrocarbon group having 1 to 4 carbon atoms.)
The component (C) is at least one organic carboxylic acid salt selected from sodium and potassium salts of aliphatic carboxylic acids having 14 to 22 carbon atoms in the hydrocarbon group.
The content ratios of the component (A), the component (B), and the component (C) are 0.1 to 15.0% by mass and 35.0 to 15.0% by mass, respectively, when the total of these components is 100% by mass. 85.0% by mass and 15.0 to 60.0% by mass.
It is characterized by not containing a multivalent metal ion.

The surface-modified resin sheet of the present invention is characterized by comprising a base layer containing a resin and a modified layer containing the modifier for the resin sheet arranged on at least one surface side of the base layer.

The method for producing a molded product of the present invention is characterized in that the surface-modified resin sheet is subjected to a molding process.

The modifier for a resin sheet of the present invention provides a modified layer having excellent antifogging property, slipperiness and antistatic property on the surface of a base resin sheet, and is suitable as a raw material for producing a surface modified resin sheet. is there. Further, since the surface-modified resin sheet of the present invention includes a modified layer containing the above-mentioned modifier for the resin sheet of the present invention, the surface of the modified layer is excellent in antifogging property, slipperiness and antistatic property. .. Therefore, by using such a surface-modified resin sheet, it is possible to efficiently manufacture a molded product such as a container having excellent antifogging property, slipperiness and antistatic property.

The modifier for a resin sheet of the present invention contains a component (A) which is an inorganic compound containing an alkali metal element, and the above components (B) and (C) . According to the present invention, a modified layer having further excellent antifogging property, slipperiness and antistatic property can be provided on at least one surface side of the base resin sheet.

Alkali metal element contained in the component (A) can lithium, sodium, potassium, rubidium, it is at least one selected from cesium. Of these, the modifiers for resin sheets of the present invention are lithium, sodium and potassium. The alkali metal element contained in the component (A) may be one or two or more.

The above component (A) is an inorganic compound and may be a halide (chloride, bromide, iodide), sulfate, nitrate, phosphate, carbonate, oxide, sulfide, hydroxide or the like. it can. Of these, the modifier for a resin sheet of the present invention is a halide and a sulfate , and chloride and a sulfate are particularly preferable.

The content ratio of the above component (A) contained in the modifier for resin sheets of the present invention is 0.1 to 15% by mass, more preferably 0.1 to 10 with respect to the total amount of the modifier for resin sheets. It is mass%.

The modifier for a resin sheet of the present invention is used to form a modified layer on at least one surface side of a base resin sheet. When forming a modified layer, it is preferable that the composition contains an adhesive component as one of the other components (hereinafter, referred to as "composition for forming a modified layer"), but that of the present invention. The modifier for a resin sheet may contain other components other than the adhesive, for example, an additive, as a component used for preparing such a composition for forming a modified layer.

When the modified layer forming composition is applied to the base resin sheet, the adhesive component is usually included together with the liquid medium from the viewpoint of the coatability. Therefore, the adhesive component is usually selected based on the liquid properties of this liquid medium. In the present invention, the composition for forming a modified layer preferably contains an aqueous liquid medium (water or a mixed solution of water and an organic solvent), and the adhesive component is preferably a hydrophilic resin. ..

The hydrophilic resin may be one that is soluble in an aqueous medium, or one that is not soluble in an aqueous medium and is dispersed therein. In the present invention, the hydrophilic resin is preferably a resin that dissolves in an aqueous medium, and is a structural unit containing a carboxylic acid (including a salt thereof) structure, a structural unit containing a hydroxy group, and a structural unit containing an amino group. , A resin containing at least one selected from a structural unit containing an amide group and a structural unit containing a quaternary ammonium structure is more preferable.

The hydrophilic resin is a compound having an acryloyl group or a methacryloyl group, and has at least one selected from a carboxylic acid (including a salt thereof) structure, a hydroxy group, an amino group, an amide group and a quaternary ammonium structure. An acrylic resin containing a structural unit derived from one or more of the compounds , specifically, an acrylic resin containing a structural unit derived from the compound represented by the following formula (1) (hereinafter, "hydrophilic acrylic resin (B)". ) ”Or“ component (B) ”). The above component (B) may contain a structural unit having no hydrophilic group.

（式中、Ｒ^１は、水素原子又はメチル基であり、Ｒ^２は、炭素原子数１〜４の２価の炭化水素基であり、Ｒ^３及びＲ^４は、互いに、同一の又は異なる、炭素原子数１〜４の炭化水素基である。） The component (B) is a compound represented by the following formula (1) from the viewpoint of adhesiveness to the base resin sheet and antifogging property, slipperiness and antistatic property of the obtained surface-modified resin sheet. It is a polymer containing a structural unit derived from (hereinafter, referred to as “structural unit (s-1)”).

(In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a divalent hydrocarbon group having 1 to 4 carbon atoms, and R ³ and R ⁴ are the same or different from each other. It is a hydrocarbon group having 1 to 4 carbon atoms.)

In the above formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² is a methylene group, an ethylene group, a trimethylene group or a tetramethylene group. R ³ and R ⁴ can be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and the like. R ³ and R ⁴ may be the same as or different from each other.

As the compound represented by the above formula (1), the following compounds are preferable.
(M1-1) A ^{compound in which R 1} is a methyl group, R ² is an ethylene group, and R ³ and R ⁴ are methyl groups (m1-2) R ¹ is a methyl group and R ² is an ethylene group. Compounds where R ³ and R ⁴ are ethyl groups (m1-3) Compounds ^{where R 1} is a hydrogen atom, R ² is an ethylene group, and R ³ and R ⁴ are ethyl groups.

When the component (B) contains the structural unit (s-1), the content ratio of the structural unit (s-1) is preferably 10 to 60 with respect to the total amount of the structural units constituting the polymer. It is mass%. The structural unit (s-1) contained in the component (B) may be only one type, or may be two or more types.

（式中、Ｒ^５は、水素原子又はメチル基であり、Ｒ^６は、ヒドロキシ基を１つ有する炭素原子数１〜４の炭化水素基、又は、ヒドロキシ基を２つ有する炭素原子数２〜４の炭化水素基である。）

（式中、Ｒ^７は、水素原子又はメチル基であり、Ｒ^８は、水素原子、又は、炭素原子数１〜１８の炭化水素基である。）

（式中、Ｒ^９は、水素原子又はメチル基であり、Ｒ^１０及びＲ^１１は、互いに、同一の若しくは異なる、水素原子、又は、炭素原子数１〜３の炭化水素基である。但し、Ｒ^１０及びＲ^１１の両方が水素原子であることを除く。） The component (B) is further divided into a structural unit derived from the compound represented by the following formula (2) (hereinafter referred to as "structural unit (s-2)") and a compound represented by the following formula (3). Derived structural unit (hereinafter referred to as "structural unit (s-3)") and structural unit derived from the compound represented by the following formula (4) (hereinafter referred to as "structural unit (s-4)") It is preferable to contain at least one selected from.

(In the formula, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a hydrocarbon group having one hydroxy group and having 1 to 4 carbon atoms, or R 6 having two hydroxy groups and having 2 to 2 carbon atoms. It is a hydrocarbon group of 4.)

(In the formula, R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.)

(In the formula, R ⁹ is a hydrogen atom or a methyl group, and R ¹⁰ and R ¹¹ are hydrogen atoms or hydrocarbon groups having 1 to 3 carbon atoms, which are the same or different from each other. Except that both R ¹⁰ and R ¹¹ are hydrogen atoms.)

In the above formula (2), R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a monohydroxyalkyl group such as a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, or a 4-hydroxybutyl group. Alternatively, it can be a dihydroxyalkyl group such as a 2,2-dihydroxyethyl group, a 2,3-dihydroxypropyl group or a 4,4-dihydroxybutyl group.

Examples of the compound represented by the above formula (2) include hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate and 3-hydroxypropyl methacrylate. , 4-Hydroxybutyl methacrylate, 2,2-dihydroxyethyl acrylate, 2,3-dihydroxypropyl acrylate, 4,4-dihydroxybutyl acrylate, 2,2-dihydroxyethyl methacrylate, 2,3-dihydroxypropyl methacrylate, 4,4 − Dihydroxybutyl methacrylate and the like can be mentioned. Of these, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferable, and 2-hydroxyethyl methacrylate is particularly preferable.

In the above formula (3), R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom or a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group or a decyl group. , Dodecyl group, hexadecyl group, octadecyl group, isooctadecyl group, cyclopentyl group, cyclohexyl group and the like.

Examples of the compound represented by the above formula (3) include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, hexadecyl acrylate, and octadecyl acrylate. Isooctadecyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, isooctadecyl methacrylate, stearyl methacrylate, cyclopentyl methacrylate. , Cyclohexyl methacrylate and the like. Of these, ethyl acrylate, methyl methacrylate and butyl acrylate are preferable, and methyl methacrylate is particularly preferable.

In the above formula (4), R ⁹ is a hydrogen atom or a methyl group, and R ¹⁰ and R ¹¹ can be a hydrogen atom or a methyl group, an ethyl group, a propyl group, an isopropyl group or the like. It should be noted that R ¹⁰ and R ¹¹ do not become hydrogen atoms at the same time.

Examples of the compound represented by the above formula (4) include N-methylacrylamide, N, N-dimethylacrylamide, N-ethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N, N-diisopropylacrylamide and the like. Can be mentioned. Of these, N, N-dimethylacrylamide is preferable.

The component (B) is a copolymer composed of a structural unit (s-1) and at least one selected from the structural units (s-2), (s-3) and (s-4). In this case, when the total amount of the structural units is 100% by mass, the content ratio of the structural units (s-1) is preferably 10 to 60% by mass from the viewpoint of antifogging property, slipperiness and antistatic property. .. The number average molecular weight of the resin having this structure is preferably 1000 to 100,000.
The number average molecular weight can be measured by a known method using an aqueous GPC (gel permeation chromatography).

Preferred copolymers as the component (B) are shown below.
(B-1) A copolymer composed of a structural unit derived from the above compound (m1-1), a structural unit derived from hydroxyethyl methacrylate, and a structural unit derived from methyl methacrylate (B-2). A copolymer (B-3) composed of a structural unit derived from m1-1), a structural unit derived from hydroxyethyl methacrylate, and a structural unit derived from methyl methacrylate. A structure derived from the above compound (m1-1). Copolymer consisting of units, structural units derived from hydroxyethyl methacrylate, and structural units derived from methyl methacrylate (B-4) Structural units derived from the above compound (m1-2), derived from hydroxyethyl methacrylate Copolymer (B-5) consisting of a structural unit derived from methyl methacrylate, a structural unit derived from the above compound (m1-3), a structural unit derived from hydroxyethyl acrylate, and ethyl acrylate Copolymer consisting of derived structural units (B-6) Structural units derived from the above compound (m1-1), structural units derived from hydroxyethyl methacrylate, and structural units derived from N, N-dimethylacrylamide. Copolymer consisting of (B-7) A copolymer (B) composed of a structural unit derived from the above compound (m1-1), a structural unit derived from hydroxyethyl methacrylate, and a structural unit derived from butyl acrylate. -8) A copolymer composed of a structural unit derived from methyl methacrylate, a structural unit derived from ethyl acrylate, a structural unit derived from butyl acrylate, and a structural unit derived from acrylic acid.

Examples of the component (B) include known methods, for example, a compound represented by the above formula (1), a compound represented by the above formula (2), a compound represented by the above formula (3), and the above formula. By dissolving at least one selected from the compounds represented by (4) in a solvent such as methanol, appropriately adding a polymerization initiator, a chain transfer agent, etc., and then carrying out a radical polymerization reaction in a nitrogen atmosphere. A synthesized one can be used.

When the modifier for a resin sheet of the present invention contains the above component (B), the content ratio thereof is preferably 35 to 85% by mass, more preferably 38, based on the total amount of the modifier for a resin sheet. ~ 65% by mass.

When the modifier for the resin sheet of the present invention is produced, the aqueous solution of the component (B) is preferably used as the production raw material for the hydrophilic resin.

As described above, the hydrophilic resin may not be dissolved in the aqueous medium but may be dispersed therein. In this case, latex, emulsion and the like can be used.

When the modifier for a resin sheet of the present invention contains an additive, examples of the additive include a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, a flame retardant, a colorant, and a mold release agent. .. The modifier for a resin sheet of the present invention contains a lubricant (hereinafter referred to as "component (C)") .

Examples of the lubricant include organic carboxylic acid, organic carboxylic acid salt, organic carboxylic acid ester, organic carboxylic acid amide, polyethylene wax, silicone oil, silica particles, silicone resin particles, talc powder and the like, and are used for the resin sheet of the present invention. The modifier may contain only one of these components, or may contain two or more of these components. In the present invention, component (C) is at least one organic carboxylate number of carbon atoms of the hydrocarbon group is selected from the sodium and potassium salts of aliphatic carboxylic acids of 14 to 22.

The organic carboxylic acid is a compound represented by R-COOH (R is a hydrocarbon group which may contain a hydroxy group), and is, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, sorbic acid. , Enantic acid, capric acid, pelargonic acid, capric acid, undecylic acid, undecylenic acid, lauric acid, tridecylic acid, myristic acid, pentadecic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, henicosyl acid, behenic acid, tricosyl Acids, lignoseric acid, oleic acid, linoleic acid, linolenic acid, erucic acid, 12-hydroxystearic acid, ricinoleic acid and the like can be mentioned. In the present invention, among these, from the viewpoint of lubricity of the surface modified resin sheet obtained, using the aliphatic carboxylic acids 14 to 22 carbon atoms (which may contain a hydroxy group). Further, salt is lithium salt, sodium salt, potassium salt, rubidium salt, a monovalent alkali metal salt is preferably in the cesium salt Iga, in the present invention, using sodium and potassium salts.

The modifier for a resin sheet of the present invention contains a component (A), a component (B) and a component (C). In this case, the content ratios of the component (A), the component (B), and the component (C) are the adhesiveness to the base resin sheet using the resin sheet modifier (composition for forming the modified layer) and the adhesiveness to the base resin sheet. From the viewpoint of antifogging property, slipperiness and antistatic property of the obtained surface-modified resin sheet, when the total of these is 100% by mass, 0.1 to 15.0% by mass and 35.0, respectively. ~ 85.0% by mass and 15.0 to 60.0% by mass, more preferably 0.1 to 10.0% by mass, 38.0 to 65.0% by mass and 30.0 to 60.0% by mass. is there.

The modifier for a resin sheet of the present invention is a raw material for producing a surface-modified resin sheet having a modified layer having excellent antifogging property, slipperiness and antistatic property on the surface of the base resin sheet. Preferably, the component (A) or the like is contained together with a liquid medium (at least one selected from water, alcohol, etc., preferably water or a mixed solution of water and alcohol having 1 to 3 carbon atoms). Therefore, it is a liquid modified layer forming composition suitable for coating on a base resin sheet. In this liquid composition, the content ratio of the liquid medium is not particularly limited.

The method for applying the modifier for a resin sheet composed of the composition for forming a liquid modified layer to the base resin sheet is not particularly limited, and a known method can be used. For example, a spray coating method, a gravure coating method, an air knife coating method, a bar coating method, a kiss coating method, a flow coating method, a dip coating method and the like can be mentioned. After applying the modifier for the resin sheet, the coating film is usually dried. The drying temperature is preferably 60 ° C to 120 ° C.

In the present invention, as the base material resin sheet to which the modifier for the resin sheet is applied, a material containing a known resin can be used. The base resin sheet is preferably a thermoplastic resin sheet, and the thermoplastic resin is, for example, 1) an aromatic vinyl resin such as polystyrene or a styrene / acrylonitrile copolymer, or 2) a polyester resin such as polyethylene terephthalate. 3) Aliper ester resin such as polylactic acid, 4) Vinyl chloride resin such as polyvinyl chloride, ethylene / vinyl chloride copolymer, 5) Acrylic resin such as polymethylmethacrylate, methylmethacrylate / styrene copolymer , 6) Polylane resin such as 6-nylon and 6,6-nylon, 7) Polycarbonate resin, 8) Polyethylene resin such as polyethylene and polypropylene. Of these, aromatic vinyl resins such as polystyrene, polyester resins such as polyethylene terephthalate, and polyolefin resins such as polypropylene are preferable. The sheet containing these thermoplastic resins may be any of an amorphous sheet, a non-stretched sheet, a simultaneous biaxially stretched sheet, a sequentially biaxially stretched sheet, and the like, and those manufactured by conventionally known sheet forming means may be used. it can. Further, the base material resin sheet may be subjected to surface treatment such as corona treatment, plasma treatment, frame treatment, chemical solution treatment with acid or alkali, if necessary. The wetting tension of the surface to which the resin sheet modifier composed of the liquid modified layer forming composition is applied, which is measured according to JIS K 6768, is not particularly limited, but is the resin sheet modifier. From the viewpoint of adhesiveness, it is preferably 35 mN / m to 70 mN / m.
The thickness of the base resin sheet is not particularly limited.

The surface-modified resin sheet of the present invention contains a base layer derived from the base resin sheet and containing a resin, and the above-mentioned modifier for the resin sheet of the present invention, which is arranged on at least one surface side of the base layer. It has a layer. Preferably, a modifier for a resin sheet composed of a liquid modified layer forming composition is applied to at least one surface side of the base resin sheet, and is particularly obtained for the resin sheet of the present invention. A resin sheet in which the modifier is adhered to the surface in an amount of ^{preferably 10 to 200} mg / m 2, more preferably 30 to 200 mg / m ² in terms of solid content per surface side.

In the surface-modified resin sheet of the present invention, the thickness of the modified layer is not particularly limited. When the surface-modified resin sheet of the present invention has modified layers on both sides, the thickness of each modified layer may be the same or different.

The surface-modified resin sheet of the present invention may be provided with a release layer on the surface of the modified layer, if necessary. The release layer may contain silicone oil, a polyoxyalkylene polymer, or the like. As a method for producing a surface-modified resin sheet in which a modified layer and a release layer are sequentially provided, after forming a modified layer on the surface of the base resin sheet, a mold release agent is applied to the surface of the modified layer. A method of applying the composition, a method of applying a resin sheet modifier containing a release agent to the surface of the base resin sheet, and then a method of migrating the release agent to the surface side. it can. When the surface-modified resin sheet of the present invention has a modified layer on only one surface side, a release layer may be provided on the side without the modified layer.

Since the surface-modified resin sheet of the present invention has excellent antifogging properties, the visibility of the article located on the opposite side through the sheet is high, and the modified layer has excellent slipperiness, so that the modified layer comes into contact with the article. In some cases, there is no damage to the article or breakage of the modified layer, and the modified layer has excellent antistatic properties, so that adhesion of dust and dirt can be suppressed. Such an action can be obtained not only in a sheet but also in a molded product obtained by processing this sheet.

The molded product can be manufactured by molding the surface-modified resin sheet of the present invention. Examples of the molding method include vacuum forming, compressed air forming and the like. In addition, the molded product can be used for lids and trays of beverage and food containers, packaging containers for electronic parts, and the like.

Hereinafter, examples will be given in order to make the configuration and effects of the present invention more specific, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, "%" and "part" are based on mass.
In the following, first, a modifier for a resin sheet (composition for forming a modified layer) containing a liquid medium is produced, and then this modifier is applied to a base resin sheet to form a surface-modified resin. Although an example of producing a sheet is shown, it goes without saying that the present invention can be a modifier for a resin sheet having a structure that does not contain a liquid medium.

1. 1. Test category 1 (raw material for modifier for resin sheet)
The raw materials used in Examples and Comparative Examples are shown.

1-1. Raw material (A)
The raw materials corresponding to the component (A) according to the present invention are as follows.
(A-1) Sodium Chloride Powder (A-2) Sodium Sulfate Powder (A-3) Potassium Chloride Powder (A-4) Lithium Chloride Powder (a-1) Magnesium Chloride Powder (a-2) Magnesium Sulfate Powder (a) -3) Calcium carbonate powder

1-2. Raw material (B)
Raw materials corresponding to the component (B) according to the present invention were obtained from the following Synthesis Examples 1 to 8.

Synthesis Example 1 (Synthesis of vinyl copolymer (B-1))
300 g of isopropanol, 65.9 g (0.42 mol) of N, N-dimethylaminoethyl methacrylate, 45.1 g (0.35 mol) of hydroxyethyl methacrylate, 90.3 g of methyl methacrylate in a reaction vessel equipped with a stirrer and a reflux device. (0.90 mol) and 1.2 g of azobisisobutyronitrile were charged, these were mixed, and a radical polymerization reaction was carried out at 80 ° C. for 3 hours under a nitrogen gas atmosphere. Next, an aqueous solution consisting of 48.7 g (0.42 mol) of monochloroacetate and 629 g of water was added dropwise to the obtained reaction solution over 10 minutes, and then the temperature was raised to 90 ° C. to add 180 g of isopropanol. Distilled away. The obtained aqueous solution was purified by an inductively coupled plasma (ICP) emission spectrophotometer using ion-exchanged water and acetone until no sodium chloride remained. Next, as a result of analyzing the reaction product in the aqueous solution, it was found that the following structural units were contained in a predetermined ratio and the number average molecular weight by GPC was 55,000. Hereinafter, this hydrophilic acrylic resin is referred to as "vinyl copolymer (B-1)".

Later, when producing a modifier for a resin sheet, an aqueous solution containing this vinyl copolymer (B-1) at a concentration of 25% (hereinafter referred to as "aqueous solution (B-1x)") was used. ..

Synthesis Examples 2 to 8 (Synthesis of vinyl copolymers (B-2) to (B-8))
Vinyl copolymers (B-2) to (B-8) were synthesized in the same manner as in Synthesis Example 1.

The vinyl copolymer (B-2) is a copolymer containing the following structural units in a predetermined ratio and having a number average molecular weight of 25,000 by GPC.

The vinyl copolymer (B-3) is a copolymer containing the following structural units in a predetermined ratio and having a number average molecular weight of 80,000 by GPC.

The vinyl copolymer (B-4) is a copolymer containing the following structural units in a predetermined ratio and having a number average molecular weight of 50,000 by GPC.

The vinyl copolymer (B-5) is a copolymer containing the following structural units in a predetermined ratio and having a number average molecular weight of 50,000 by GPC.

The vinyl copolymer (B-6) is a copolymer containing the following structural units in a predetermined ratio and having a number average molecular weight of 12000 by GPC.

The vinyl copolymer (B-7) is a copolymer containing the following structural units in a predetermined ratio and having a number average molecular weight of 45,000 by GPC.

The vinyl copolymer (B-8) is a copolymer containing the following structural units in a predetermined ratio and having a number average molecular weight of 40,000 by GPC.

Then, an aqueous solution containing these vinyl copolymers (B-2) to (B-8) at a concentration of 25% (hereinafter, "aqueous solution (B-2x)" to "aqueous solution (B-8x""). ) Was used.

1-3. Raw material (C)
The raw materials corresponding to the component (C) according to the present invention are as follows.
(C-1) Sodium octadecate powder (C-2) Sodium octadecate powder (C-3) Sodium hexadecenoate powder (C-4) Potassium octadecate powder (C-5) Potassium octadecate powder (C-6) Sodium tetradecanoate powder (C-7) Potassium docosenoate powder

2. Test category 2 (Preparation of modifier for resin sheet)
Using the raw materials shown in Test Category 1, a modifier for a resin sheet, which comprises a liquid modified layer-forming composition for coating on a base resin sheet, was prepared (see Table 1). In the following experiments, an aqueous solution (B-1x) of a vinyl copolymer (B-1) was used as a raw material for producing a liquid modified layer forming composition, but as described above, it was not an aqueous solution. It is also possible to prepare a modifier for a resin sheet using only an isolated vinyl copolymer that does not contain a liquid medium.

Example 1-1
8.0 parts of water, 4.4 parts of aqueous solution (B-1x), 0.8 parts of sodium octadecanoate (C-1), and 0.1 parts of sodium chloride (A-1) are mixed. Then, a modifier (E-1) for a resin sheet having a solid content of 15% was prepared. In this modifier for resin sheet (E-1), the solid content ratio (mass ratio) of the alkali metal-containing inorganic compound / hydrophilic acrylic resin / organic carboxylate is 5/55/40.

Example 1-2～1- 11, Reference Examples 1-1～1-2 and Comparative Examples 1-1 to 1-6
Using the raw materials in Table 1, the modifiers (E-2) to (E- 11 ) , (EE-1) to (EE-2) and (e-1) to (e-1) to (e-1) to (E-1) e-6) was prepared.

3. 3. Test category 3 (Manufacturing and evaluation of surface-modified resin sheet)
A coating liquid was prepared using the resin sheet modifier produced in Test Category 2, and then the surface-modified resin sheet shown in Table 2 was produced using this coating liquid and the base resin sheet. .. The base resin sheet used is shown below.
(S-1) Polyester resin sheet (polyethylene terephthalate resin uncrystallized type)
(S-2) Polyester resin sheet (polyethylene terephthalate resin biaxially stretched type)
(S-3) Aliphatic ester resin sheet (non-stretching type, corona treatment with a wetting tension equivalent to JIS K 6768 of 44 mN / m)
(S-4) Polystyrene resin sheet (non-stretching type, corona treatment with a wetting tension equivalent to JIS K 6768 of 44 mN / m)
(S-5) Polystyrene resin sheet (biaxially stretched type, with a wetting tension of 44 mN / m according to JIS K 6768 by corona treatment)
(S-6) Polyolefin-based resin sheet (polypropylene, non-stretching type, corona treatment with a wetting tension equivalent to JIS K 6768 of 44 mN / m)
(S-7) Polymethyl methacrylate sheet (non-stretching type, corona treatment with a wetting tension equivalent to JIS K 6768 of 44 mN / m)

Example 2-1
13.3 g of the resin sheet modifier (E-1) having a solid content of 15% prepared in Example 1-1 and 86.7 g of a solvent of water / isopropyl alcohol = 90/10 (mass ratio) are mixed. Therefore, a coating liquid having an effective concentration of 2% was prepared.
Then, the prepared coating liquid was applied to the polyester resin sheet (S-1) with a bar coater (application amount: 5 g / m ² ). Then, the coating film was dried at 70 ° C. to prepare a surface-modified resin sheet (P-1) having a modified layer having ^{an absolute dry coating amount of 100 mg / m 2.}
Next, the obtained surface-modified resin sheet (P-1) was evaluated for antifogging property, slipperiness and antistatic property on the surface of the modified layer. The results are also shown in Table 2.

(1) Anti-fog property A surface-modified resin sheet is cut into a circle with a diameter of 7 cm and covered with a 200 ml beaker containing 100 ml of hot water at 60 ° C so that the surface of the modified layer is inside the beaker at 5 ° C. It was left in the refrigerator for 24 hours. Then, the degree of adhesion of water droplets on the surface of the modified layer of the surface-modified resin sheet was observed, and the antifogging property was evaluated according to the following criteria.
<Evaluation criteria for anti-fog>
⊚: Transparent with no water droplets attached (excellent anti-fog property)
◯: There was large water droplets attached, but it was transparent (good anti-fog property).
Δ: Slightly opaque due to adhesion of water droplets (poor anti-fog property)
X: It was opaque due to the adhesion of small water droplets (the anti-fog property was extremely poor and it was not practical).

(2) Slippery The coefficient of dynamic friction on the surface of the modified layer was measured according to JIS-K7125, and the slipperiness was evaluated according to the following criteria.
<Evaluation criteria for slipperiness>
⊚: Dynamic friction coefficient was less than 0.25 ○: Dynamic friction coefficient was 0.25 or more and less than 0.30 Δ: Dynamic friction coefficient was 0.30 or more and less than 0.35 ×: Dynamic friction coefficient was 0 It was .35 or more

(3) Antistatic property The surface-modified resin sheet was placed on the surface-modified resin sheet under the conditions of a temperature of 20 ° C. and a relative humidity of 65% for 24 hours to adjust the humidity, and then the surface resistivity (Ω) was measured under the same conditions. The measuring device is a surface resistance value measuring device (trade name: Megaresta HT-301) manufactured by Sisid Electric Co., Ltd. From the surface resistance value, the antistatic property was evaluated according to the following criteria.
<Evaluation criteria for antistatic properties>
⊚: Surface resistivity was ^{less than 5.0 × 10 8} Ω ○: Surface resistivity was 5.0 × 10 ⁸ Ω or more and ^{less than 1.0 × 10 9} Ω Δ: Surface resistivity was 1. 0 × 10 ⁹ Ω or more and ^{less than 5.0 × 10 9} Ω ×: Surface resistivity was 5.0 × 10 ⁹ Ω or more

Example 2-2～2- 11, Reference Examples 2-1 to 2-2 and Comparative Examples 2-1 to 2-6
Instead of the resin sheet modifier (E-1), the resin sheet modifiers (E-2) to (E- 11 ) , (EE-1) to (EE-2) and (e-1) Each coating liquid was prepared in the same manner as in Example 2-1 except that (e-6) was used. Next, the coating liquid is applied to the surface of the base resin sheet shown in Table 2, and the surface-modified resin sheets (P-2) to (P- 11 ) and (PP-1) to provided with the modified layer are provided. (PP-2) and (p-1) to (p-6) were obtained.
Then, the surface-modified resin sheet was evaluated in the same manner as in Example 2-1. The results are also shown in Table 2.

4. Test category 4 (manufacturing of molded products)
The surface-modified resin sheet produced in Test Category 3 is subjected to pneumatic molding, and a pyramid-shaped molded product (opening: 70 mm × 70 mm, bottom: 60 mm × 60 mm, depth: 30 mm) having the modified layer as the inner surface. ) Was manufactured.

Example 3-1
The surface-modified resin sheet (P-1) obtained in Example 2-1 was processed by a compressed air molding machine to prepare a pyramid-shaped molded product. No problems such as peeling of the modified layer were observed, and the appearance was good.

Examples 3-2-3-11 and Reference Examples 3-1-3-2
Using the surface-modified resin sheet shown in Table 2, a pyramid-shaped molded product was produced in the same manner as in Example 3-1. No problems such as peeling of the modified layer were observed in any of the molded products, and the appearance was good.

By applying the modifier for a resin sheet of the present invention to the surface of a base resin sheet, a surface-modified resin sheet having a modified layer having excellent antifogging property, slipperiness and antistatic property can be produced. Can be done. Since the surface-modified resin sheet of the present invention is excellent in antifogging property, slipperiness and antistatic property on the surface of the modified layer, such a surface-modified resin sheet is used for antifogging property, slipperiness and antistatic property. Molded products such as containers with excellent antistatic properties can be efficiently manufactured. The surface-modified resin sheet and the molded product are suitable for a wide range of applications such as food packaging materials, food packaging containers, and packaging containers for electronic materials.

Claims (6)

A modifier used to modify the surface of a resin sheet.
(A) Inorganic compounds containing alkali metal elements,
(B) Hydrophilic acrylic resin and
(C) Contains lubricant,
Wherein component (A), Ri least 1 Tsudea selected from lithium, halides and sulfates of sodium or potassium,
The component (B) is a polymer containing a structural unit derived from a compound represented by the following formula (1).

(In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a divalent hydrocarbon group having 1 to 4 carbon atoms, and R ³ and R ⁴ are the same or different from each other. It is a hydrocarbon group having 1 to 4 carbon atoms.)
The component (C) is at least one organic carboxylic acid salt selected from sodium and potassium salts of aliphatic carboxylic acids having 14 to 22 carbon atoms in the hydrocarbon group.
The content ratios of the component (A), the component (B), and the component (C) are 0.1 to 15.0% by mass and 35.0 to 15.0% by mass, respectively, when the total of these is 100% by mass. 85.0% by mass and 15.0 to 60.0% by mass.
A modifier for resin sheets, which is characterized by not containing multivalent metal ions. The component (B) is further represented by a structural unit derived from a compound represented by the following formula (2), a structural unit derived from a compound represented by the following formula (3), and a following formula (4). The modifier for a resin sheet according to claim 1 , which comprises at least one selected from structural units derived from the compound to be used.

(In the formula, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a hydrocarbon group having one hydroxy group and having 1 to 4 carbon atoms, or R 6 having two hydroxy groups and having 2 to 2 carbon atoms. It is a hydrocarbon group of 4.)

(In the formula, R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.)

(In the formula, R ⁹ is a hydrogen atom or a methyl group, and R ¹⁰ and R ¹¹ are hydrogen atoms or hydrocarbon groups having 1 to 3 carbon atoms, which are the same or different from each other. Except that both R ¹⁰ and R ¹¹ are hydrogen atoms.) The modifier for a resin sheet according to claim 1 or 2 , wherein the number average molecular weight of the component (B) is 1000 to 100,000. It is characterized by comprising a base layer containing a resin and a modified layer containing the modifier for a resin sheet according to any one of claims 1 to 3 , which is arranged on at least one surface side of the base layer. Surface modified resin sheet. The surface-modified resin sheet according to claim 4 , wherein the resin contained in the base layer is at least one selected from a polyester resin, an aromatic vinyl resin, and an olefin resin. A method for producing a molded product, which comprises subjecting the surface-modified resin sheet according to claim 4 or 5 to a molding process.