KR20210113625A - Modifier for resin sheet, method for manufacturing surface-modified resin sheet and molded article - Google Patents

Modifier for resin sheet, method for manufacturing surface-modified resin sheet and molded article Download PDF

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KR20210113625A
KR20210113625A KR1020217023833A KR20217023833A KR20210113625A KR 20210113625 A KR20210113625 A KR 20210113625A KR 1020217023833 A KR1020217023833 A KR 1020217023833A KR 20217023833 A KR20217023833 A KR 20217023833A KR 20210113625 A KR20210113625 A KR 20210113625A
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South Korea
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resin sheet
modifier
resin
component
group
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KR1020217023833A
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Korean (ko)
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KR102594917B1 (en
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준스케 후지이
마키코 오자와
아키오 하타
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다케모토 유시 가부시키 가이샤
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C08K2003/3063—Magnesium sulfate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

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  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

본 발명의 목적은, 1면측에 배치된 개질층에 있어서 방담성, 미끄럼성 및 대전 방지성이 우수한 표면 개질 수지 시트 및 그의 개질층의 형성 재료로서 적합한 수지 시트용 개질제, 그리고 성형품의 제조 방법을 제공하는 것이다. 본 발명의 수지 시트용 개질제는, (A) 알칼리 금속 원소(리튬, 나트륨 또는 칼륨)를 포함하는 무기 화합물을 함유하는 것을 특징으로 한다. 또한, (B) 친수성 아크릴 수지, (C) 활제 등을 함유할 수 있다.An object of the present invention is to provide a surface-modified resin sheet having excellent antifogging properties, slipping properties and antistatic properties in a modified layer disposed on one side, a modifier for a resin sheet suitable as a material for forming the modified layer thereof, and a method for producing a molded article will provide The modifier for resin sheets of this invention contains the inorganic compound containing (A) an alkali metal element (lithium, sodium, or potassium), It is characterized by the above-mentioned. Moreover, (B) hydrophilic acrylic resin, (C) a lubricant, etc. can be contained.

Description

수지 시트용 개질제, 표면 개질 수지 시트 및 성형품의 제조 방법Modifier for resin sheet, method for manufacturing surface-modified resin sheet and molded article

본 발명은 1면측에 배치된 개질층에 있어서, 방담성, 미끄럼성 및 대전 방지성이 우수한 표면 개질 수지 시트 및 그의 개질층의 형성 재료로서 적합한 수지 시트용 개질제에 관한 것이다. 또한, 본 발명은 그 표면 개질 수지 시트를 사용해서 성형품을 제조하는 방법에 관한 것이다.The present invention relates to a surface-modified resin sheet having excellent antifogging properties, slipping properties and antistatic properties in a modified layer disposed on one side, and a modifier for a resin sheet suitable as a material for forming the modified layer thereof. Further, the present invention relates to a method for manufacturing a molded article using the surface-modified resin sheet.

종래, 박육의 수지 성형품(시트, 용기 등)은 각종 부품, 식품 등의 제품을 포장하기 위해서 널리 사용되고 있다. 그리고 식품, 전자 부품 등을 포장하는 경우에는, 상기 포장용 성형품의 특히 내면측에 있어서, 방담성, 미끄럼성, 대전 방지성 등이 필요하게 되는 경우가 있다.BACKGROUND ART Conventionally, thin resin molded articles (sheets, containers, etc.) have been widely used for packaging various parts and products such as food. And when packaging foodstuffs, electronic parts, etc., especially in the inner surface side of the said packaging molded article, antifogging property, slip property, antistatic property, etc. may be required.

이들 성능을 부여하기 위해서, 이하의 기술이 알려져 있다.In order to impart these properties, the following techniques are known.

예를 들어 특허문헌 1에는, 방담성 및 대전 방지성을 부여하기 위해서, 특정한 구조를 갖고 수 평균 분자량이 10000 내지 100000인 비닐 공중합체와, 유기 카르복실산, 유기 카르복실산염, 유기 카르복실산에스테르, 유기 카르복실산아미드, 폴리에틸렌 왁스, 실리콘 오일, 실리카 입자, 실리콘 수지 입자 및 탈크 분말에서 선택되는 하나 또는 둘 이상의 활제를, 30/70 내지 90/10(중량비)의 비율로 함유하는 것을 특징으로 하는 합성 고분자 필름용 표면 처리제가 개시되어 있다.For example, in patent document 1, in order to provide antifogging property and antistatic property, it has a specific structure and the vinyl copolymer whose number average molecular weights are 10000-100000, organic carboxylic acid, organic carboxylate, organic carboxylic acid One or more lubricants selected from esters, organic carboxylic acid amides, polyethylene wax, silicone oil, silica particles, silicone resin particles and talc powder are contained in a ratio of 30/70 to 90/10 (weight ratio) A surface treatment agent for a synthetic polymer film is disclosed.

특허문헌 2에는, 기재 수지 시트에 도포하는 방담제로서, 자당과, 탄소수 1 2 내지 22의 지방족 모노카르복실산의 부분 에스테르 화합물, 및 탄소수 14 내지 22의 지방족 모노카르복실산 알칼리 금속염을 함유하는 방담제가 개시되어 있다.Patent Document 2 discloses, as an antifogging agent applied to a base resin sheet, sucrose, a partial ester compound of an aliphatic monocarboxylic acid having 12 to 22 carbon atoms, and an alkali metal salt of an aliphatic monocarboxylic acid having 14 to 22 carbon atoms. Antifogging agents are disclosed.

또한, 특허문헌 3에는 비이온성 계면 활성제 등을 포함하는 방담제 (A)와, 2차 성형의 가열 온도를 T℃라 했을 때, (T-90)℃ 내지 (T＋20)℃의 연화점을 갖는 친수성 (메트)아크릴계 중합체 (B1)을 포함하는 방담 보조제 (B)를 함유하는 방담층용 도공액이 개시되어 있다. 그리고, 이 도공액은 금속 화합물 (D)를 함유할 수 있고, 특히 다가의 금속 이온의 화합물(염화마그네슘 등)이 바람직하다고 기재되어 있다.In addition, Patent Document 3 describes an antifogging agent (A) containing a nonionic surfactant or the like, and a hydrophilicity having a softening point of (T-90)°C to (T+20)°C when the heating temperature of secondary molding is T°C. The coating liquid for antifogging layers containing the antifogging auxiliary agent (B) containing a (meth)acrylic-type polymer (B1) is disclosed. And it is described that this coating liquid can contain a metal compound (D), and especially the compound (magnesium chloride etc.) of a polyvalent metal ion is preferable.

일본특허공개 제2004-244605호 공보Japanese Patent Laid-Open No. 2004-244605 일본특허공개 제2007-031545호 공보Japanese Patent Laid-Open No. 2007-031545 일본특허공개 제2018-176740호 공보Japanese Patent Laid-Open No. 2018-176740

근년, 식품, 전자 부품 등의 포장 용기나 수지 시트에 대하여, 방담성 및 미끄럼성에 더하여 보다 고레벨의 대전 방지성이 요구되고 있다.In recent years, in addition to antifogging properties and sliding properties, high-level antistatic properties are required for packaging containers and resin sheets for food and electronic parts.

본 발명이 해결하고자 하는 과제는, 적어도 1면측에 배치된 개질층에 있어서, 방담성, 미끄럼성 및 대전 방지성이 우수한 표면 개질 수지 시트 및 그의 개질층의 형성 재료로서 적합한 수지 시트용 개질제를 제공하는 것이다. 또한, 기타 과제는, 이러한 표면 개질 수지 시트를 사용해서 용기 등의 성형품을 제조하는 방법을 제공하는 것이다. 본 명세서에 있어서 「방담성」은, 함수성 또는 표면에 수분이 부착되어 있는 물품을 표면 개질 수지 시트에 의해(개질층을 물품측으로 하여) 포장한 상태에서, 예를 들어 5℃ 이하의 분위기 하에 적재하고 방치한 후, 개질층의 표면에 잔존하기 쉬운 수적이 거의 보이지 않고, 시트를 통해서 물품을 양호하게 시인할 수 있는 성능을 말한다.The problem to be solved by the present invention is to provide a surface-modified resin sheet having excellent anti-fogging properties, slipping properties and antistatic properties in a modified layer disposed on at least one surface side, and a modifier for a resin sheet suitable as a material for forming the modified layer thereof will do Moreover, another subject is providing the method of manufacturing molded articles, such as a container, using such a surface modification resin sheet. In the present specification, "anti-fogging" refers to a state in which a water-containing or moisture-adhering article is packaged with a surface-modified resin sheet (with the modified layer on the article side), for example, in an atmosphere of 5° C. or less. It refers to the performance that, after stacking and leaving to stand, hardly any water droplets likely to remain on the surface of the modified layer can be seen, and the article can be visually recognized through the sheet.

본 발명자들은 예의 연구한 결과, 알칼리 금속 원소를 포함하는 무기 화합물을 함유하는 수지 시트용 개질제를 포함하는 층(개질층)을 기재 수지 시트의 표면에 형성시켜서 얻어진 표면 개질 수지 시트가 방담성, 미끄럼성 및 대전 방지성이 우수한 것을 발견했다.As a result of intensive research by the present inventors, the surface-modified resin sheet obtained by forming a layer (modified layer) containing a modifier for a resin sheet containing an inorganic compound containing an alkali metal element on the surface of the base resin sheet has anti-fogging properties and anti-slip properties. It was discovered that it was excellent in antistatic property and antistatic property.

본 발명은 이하에 나타내진다.The present invention is shown below.

본 발명의 수지 시트용 개질제는 수지 시트(이하, 「기재 수지 시트」라고 한다)의 표면 개질에 사용되는 개질제이며, 알칼리 금속 원소를 포함하는 무기 화합물 (A)를 함유하는 것을 특징으로 한다.The modifier for resin sheets of the present invention is a modifier used for surface modification of a resin sheet (hereinafter referred to as "base resin sheet"), and is characterized by containing an inorganic compound (A) containing an alkali metal element.

본 발명의 수지 시트용 개질제는, 추가로 친수성 아크릴 수지 (B) 및 유기 카르복실산염 (C) 중 적어도 한쪽을 함유하는 것이 바람직하다.It is preferable that the modifier for resin sheets of this invention contains at least one of a hydrophilic acrylic resin (B) and an organic carboxylate (C) further.

본 발명의 표면 개질 수지 시트는, 수지를 포함하는 기층과, 해당 기층의 적어도 1면측에 배치된, 상기 수지 시트용 개질제를 포함하는 개질층을 구비하는 것을 특징으로 한다.The surface-modified resin sheet of the present invention is characterized by comprising a base layer comprising a resin, and a modifier layer comprising the modifier for a resin sheet disposed on at least one side of the base layer.

본 발명의 성형품의 제조 방법은 상기 표면 개질 수지 시트를 성형 가공에 제공하는 것을 특징으로 한다.The method for producing a molded article of the present invention is characterized in that the surface-modified resin sheet is subjected to a molding process.

본 발명의 수지 시트용 개질제는 기재 수지 시트의 표면에 방담성, 미끄럼성 및 대전 방지성이 우수한 개질층을 부여하고, 표면 개질 수지 시트를 제조하는 원료로서 적합하다. 또한, 본 발명의 표면 개질 수지 시트는 상기 본 발명의 수지 시트용 개질제를 포함하는 개질층을 구비하기 때문에, 이 개질층의 표면에 있어서 방담성, 미끄럼성 및 대전 방지성이 우수하다. 따라서, 이러한 표면 개질 수지 시트를 사용하여, 방담성, 미끄럼성 및 대전 방지성이 우수한 용기 등의 성형품을 효율적으로 제조할 수 있다.The modifier for a resin sheet of the present invention provides a modified layer excellent in antifogging property, slip property and antistatic property to the surface of the base resin sheet, and is suitable as a raw material for manufacturing the surface-modified resin sheet. Further, since the surface-modified resin sheet of the present invention includes a modified layer containing the modifier for a resin sheet of the present invention, the surface of the modified layer is excellent in antifogging properties, sliding properties and antistatic properties. Therefore, using such a surface-modified resin sheet, molded articles such as containers having excellent anti-fogging properties, sliding properties and antistatic properties can be efficiently manufactured.

본 발명의 수지 시트용 개질제는, 알칼리 금속 원소를 포함하는 무기 화합물인 성분 (A)를 함유한다. 본 발명에 있어서 수지 시트용 개질제가 다른 성분(후술)을 함유함으로써, 기재 수지 시트의 적어도 1면측에, 방담성, 미끄럼성 및 대전 방지성이 더 우수한 개질층을 부여할 수 있다.The modifier for resin sheets of this invention contains the component (A) which is an inorganic compound containing an alkali metal element. In the present invention, when the modifier for resin sheets contains other components (described later), a modified layer further excellent in antifogging properties, slip properties and antistatic properties can be provided on at least one side of the base resin sheet.

상기 성분 (A)에 포함되는 알칼리 금속 원소는 특별히 한정되지 않고, 리튬, 나트륨, 칼륨, 루비듐, 세슘 등에서 선택된 적어도 하나로 할 수 있다. 이들 중, 바람직한 원소는 리튬, 나트륨 및 칼륨이다. 또한, 상기 성분 (A)에 포함되는 알칼리 금속 원소는 하나나 둘 이상이어도 된다.The alkali metal element contained in the component (A) is not particularly limited, and may be at least one selected from lithium, sodium, potassium, rubidium, cesium, and the like. Among these, preferred elements are lithium, sodium and potassium. In addition, the alkali metal element contained in the said component (A) may be one, two or more may be sufficient.

상기 성분 (A)는 무기 화합물이며, 할로겐화물(염화물, 브롬화물, 요오드화물), 황산염, 질산염, 인산염, 탄산염, 산화물, 황화물, 수산화물 등으로 할 수 있다. 이들 중, 할로겐화물 및 황산염이 바람직하고, 염화물 및 황산염이 특히 바람직하다.The component (A) is an inorganic compound and can be a halide (chloride, bromide, iodide), sulfate, nitrate, phosphate, carbonate, oxide, sulfide, hydroxide or the like. Of these, halides and sulfates are preferable, and chlorides and sulfates are particularly preferable.

본 발명의 수지 시트용 개질제에 포함되는 상기 성분 (A)의 함유 비율은, 수지 시트용 개질제의 전체에 대하여 바람직하게는 0.1 내지 15질량%, 보다 바람직하게는 0.1 내지 10질량%이다.Preferably the content rate of the said component (A) contained in the modifier for resin sheets of this invention is 0.1-15 mass % with respect to the whole modifier for resin sheets, More preferably, it is 0.1-10 mass %.

본 발명의 수지 시트용 개질제는 기재 수지 시트의 적어도 1면측에 개질층을 형성하기 위해서 사용되는 것이다. 개질층을 형성하는 경우에는, 다른 성분의 하나로서, 접착제 성분을 함유하는 조성물(이하, 「개질층 형성용 조성물」이라고 한다)인 것이 바람직하지만, 본 발명의 수지 시트용 개질제는 이러한 개질층 형성용 조성물의 조제에 사용되는 성분으로서, 접착제 이외의 다른 성분, 예를 들어 첨가제를 아울러 포함하는 것이어도 된다.The modifier for resin sheets of the present invention is used to form a modified layer on at least one side of the base resin sheet. In the case of forming the modified layer, as one of the other components, a composition containing an adhesive component (hereinafter referred to as "composition for forming a modified layer") is preferable. As a component used for preparation of the composition for use, other components other than the adhesive, for example, may also contain additives.

상기 접착제 성분은 개질층 형성용 조성물을 기재 수지 시트에 도포하는 경우에, 그의 도포성의 관점에서 통상, 액상 매체와 함께 아울러 포함된다. 그 때문에, 상기 접착제 성분은 통상, 이 액상 매체의 액성에 따라 선택된다. 본 발명에 있어서, 개질층 형성용 조성물은 수성의 액상 매체(물, 또는 물 및 유기 용제의 혼합액)를 포함하는 것이 바람직하고, 상기 접착제 성분은 바람직하게는 친수성 수지이다.The said adhesive component is normally contained together with a liquid medium from a viewpoint of the applicability|paintability, when apply|coating the composition for modifying layer formation to a base resin sheet. Therefore, the adhesive component is usually selected according to the liquidity of the liquid medium. In the present invention, the composition for forming a modified layer preferably contains an aqueous liquid medium (water or a mixture of water and an organic solvent), and the adhesive component is preferably a hydrophilic resin.

상기 친수성 수지는 수성 매체에 용해되는 것이어도 되고, 수성 매체에 용해되지 않고, 그 중에서 분산되는 것이어도 된다. 본 발명에 있어서는, 상기 친수성 수지는 수성 매체에 용해되는 수지인 것이 바람직하고, 카르복실산(그의 염을 포함한다) 구조를 포함하는 구조 단위, 히드록시기를 포함하는 구조 단위, 아미노기를 포함하는 구조 단위, 아미드기를 포함하는 구조 단위 및 4급 암모늄 구조를 포함하는 구조 단위에서 선택된 적어도 1종을 포함하는 수지인 것이 보다 바람직하다.The hydrophilic resin may be dissolved in the aqueous medium or may be dispersed in the aqueous medium without being dissolved. In the present invention, the hydrophilic resin is preferably a resin soluble in an aqueous medium, and a structural unit containing a carboxylic acid (including a salt thereof) structure, a structural unit containing a hydroxyl group, and a structural unit containing an amino group , It is more preferable that it is a resin containing at least 1 sort(s) selected from the structural unit containing the structural unit containing an amide group, and the structural unit containing a quaternary ammonium structure.

상기 친수성 수지는 특히 바람직하게는 아크릴로일기 또는 메타크릴로일기를 갖는 화합물이며, 카르복실산(그의 염을 포함한다) 구조, 히드록시기, 아미노기, 아미드기 및 4급 암모늄 구조에서 선택된 적어도 1종을 갖는 화합물의 1종 또는 2종 이상에서 유래하는 구조 단위를 포함하는 아크릴 수지(이하, 「친수성 아크릴 수지 (B)」 또는 「성분 (B)」라고 한다)이다. 상기 성분 (B)는 친수성기를 갖지 않는 구조 단위를 포함해도 된다.The hydrophilic resin is particularly preferably a compound having an acryloyl group or a methacryloyl group, and contains at least one selected from a carboxylic acid (including its salt) structure, a hydroxyl group, an amino group, an amide group, and a quaternary ammonium structure. It is an acrylic resin (henceforth "hydrophilic acrylic resin (B)" or "component (B)") containing the structural unit derived from 1 type, or 2 or more types of the compound which has. The said component (B) may also contain the structural unit which does not have a hydrophilic group.

상기 성분 (B)는 기재 수지 시트에 대한 접착성, 그리고 얻어지는 표면 개질 수지 시트에 있어서의 방담성, 미끄럼성 및 대전 방지성의 관점에서, 하기 식 (1)로 표시되는 화합물에서 유래하는 구조 단위(이하, 「구조 단위 (s-1)」이라고 한다)를 포함하는 중합체인 것이 바람직하다.The component (B) is a structural unit derived from a compound represented by the following formula (1) from the viewpoint of adhesion to the base resin sheet, and antifogging properties, sliding properties and antistatic properties in the surface-modified resin sheet obtained ( Hereinafter, it is preferable that it is a polymer containing "structural unit (s-1)").

Figure pct00001
Figure pct00001

(식 중, R1은 수소 원자 또는 메틸기이고, R2는 탄소 원자수 1 내지 4의 2가의 탄화수소기이고, R3 및 R4는 서로 동일하거나 또는 상이한, 탄소 원자수 1 내지 4의 탄화수소기이다.)(Wherein, 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, a hydrocarbon group having 1 to 4 carbon atoms. am.)

상기 식 (1)에 있어서, R1은 수소 원자 또는 메틸기이고, R2는 메틸렌기, 에틸렌기, 트리메틸렌기 또는 테트라메틸렌기이다. R3 및 R4는 메틸기, 에틸기, 프로필기, 이소프로필기, 부틸기, 이소부틸기 등으로 할 수 있다. R3 및 R4는 서로 동일해도 되고, 상이해도 된다.In the 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, or the like. R 3 and R 4 may be the same as or different from each other.

상기 식 (1)로 표시되는 화합물로서는, 이하의 화합물이 바람직하다.As a compound represented by said Formula (1), the following compounds are preferable.

(m1-1) R1이 메틸기이고, R2가 에틸렌기이고, R3 및 R4가 메틸기인 화합물(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 a methyl group

(m1-2) R1이 메틸기이고, R2가 에틸렌기이고, R3 및 R4가 에틸기인 화합물(m1-2) A compound in which R 1 is a methyl group, R 2 is an ethylene group, and R 3 and R 4 are an ethyl group

(m1-3) R1이 수소 원자이고, R2가 에틸렌기이고, R3 및 R4가 에틸기인 화합물(m1-3) A compound in which R 1 is a hydrogen atom, R 2 is an ethylene group, and R 3 and R 4 are an ethyl group

상기 성분 (B)가 상기 구조 단위 (s-1)을 포함하는 경우, 이 구조 단위 (s-1)의 함유 비율은, 중합체를 구성하는 구조 단위의 전량에 대하여 바람직하게는 10 내지 60질량%이다. 또한, 상기 성분 (B)에 포함되는 상기 구조 단위 (s-1)은 1종만이어도 되고, 2종 이상이어도 된다.When the component (B) contains the structural unit (s-1), the content of the structural unit (s-1) is preferably 10 to 60% by mass based on the total amount of the structural units constituting the polymer. am. In addition, the number of the said structural unit (s-1) contained in the said component (B) may be one, and 2 or more types may be sufficient as it.

상기 성분 (B)는 추가로, 하기 식 (2)로 표시되는 화합물에서 유래하는 구조 단위(이하, 「구조 단위 (s-2)」라고 한다), 하기 식 (3)으로 표시되는 화합물에서 유래하는 구조 단위(이하, 「구조 단위 (s-3)」이라고 한다) 및 하기 식 (4)로 표시되는 화합물에서 유래하는 구조 단위(이하, 「구조 단위 (s-4)」라고 한다)에서 선택된 적어도 1종을 포함하는 것이 바람직하다.The component (B) is further derived from a structural unit derived from a compound represented by the following formula (2) (hereinafter referred to as “structural unit (s-2)”), a compound represented by the following formula (3) a structural unit (hereinafter referred to as "structural unit (s-3)") and a structural unit derived from a compound represented by the following formula (4) (hereinafter referred to as "structural unit (s-4)") It is preferable to include at least 1 type.

Figure pct00002
Figure pct00002

(식 중, R5는 수소 원자 또는 메틸기이고, R6은 히드록시기를 1개 갖는 탄소 원자수 1 내지 4의 탄화수소기, 또는 히드록시기를 2개 갖는 탄소 원자수 2 내지 4의 탄화수소기이다.)(Wherein, R 5 is a hydrogen atom or a methyl group, and R 6 is a hydrocarbon group having 1 to 4 carbon atoms having one hydroxyl group, or a hydrocarbon group having 2 to 4 carbon atoms having two hydroxyl groups.)

Figure pct00003
Figure pct00003

(식 중, R7은 수소 원자 또는 메틸기이고, R8은 수소 원자, 또는 탄소 원자수 1 내지 18의 탄화수소기이다.)(Wherein, 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.)

Figure pct00004
Figure pct00004

(식 중, R9는 수소 원자 또는 메틸기이고, R10 및 R11은 서로 동일하거나 혹은 상이한, 수소 원자, 또는 탄소 원자수 1 내지 3의 탄화수소기이다. 단, R10 및 R11의 양쪽이 수소 원자인 것을 제외한다.)(Wherein, R 9 is a hydrogen atom or a methyl group, and R 10 and R 11 are the same or different from each other, a hydrogen atom, or a hydrocarbon group having 1 to 3 carbon atoms. However, both R 10 and R 11 are Except for hydrogen atoms.)

상기 식 (2)에 있어서, R5는 수소 원자 또는 메틸기이고, R6은 히드록시메틸기, 2-히드록시에틸기, 3-히드록시프로필기, 4-히드록시부틸기 등의 모노히드록시알킬기, 또는 2,2-디히드록시에틸기, 2,3-디히드록시프로필기, 4,4-디히드록시부틸기 등의 디히드록시알킬기로 할 수 있다.In the formula (2), R 5 is a hydrogen atom or a methyl group, R 6 is a monohydroxyalkyl group such as a hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, or 4-hydroxybutyl group; or a dihydroxyalkyl group such as a 2,2-dihydroxyethyl group, a 2,3-dihydroxypropyl group or a 4,4-dihydroxybutyl group.

상기 식 (2)로 표시되는 화합물로서는, 히드록시메틸아크릴레이트, 2-히드록시에틸아크릴레이트, 3-히드록시프로필아크릴레이트, 4-히드록시부틸아크릴레이트, 히드록시메틸메타크릴레이트, 2-히드록시에틸메타크릴레이트, 3-히드록시프로필메타크릴레이트, 4-히드록시부틸메타크릴레이트, 2,2-디히드록시에틸아크릴레이트, 2,3-디히드록시프로필아크릴레이트, 4,4-디히드록시부틸아크릴레이트, 2,2-디히드록시에틸메타크릴레이트, 2,3-디히드록시프로필메타크릴레이트, 4,4-디히드록시부틸메타크릴레이트 등을 들 수 있다. 이들 중, 2-히드록시에틸아크릴레이트 및 2-히드록시에틸메타크릴레이트가 바람직하고, 2-히드록시에틸메타크릴레이트가 특히 바람직하다.Examples of the compound represented by the formula (2) include hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, hydroxymethyl methacrylate, 2- Hydroxyethyl methacrylate, 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, etc. are mentioned. Of these, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferable, and 2-hydroxyethyl methacrylate is particularly preferable.

상기 식 (3)에 있어서, R7은 수소 원자 또는 메틸기이고, R8은 수소 원자, 또는 메틸기, 에틸기, 프로필기, 이소프로필기, 부틸기, 헥실기, 옥틸기, 데실기, 도데실기, 헥사데실기, 옥타데실기, 이소옥타데실기, 시클로펜틸기, 시클로헥실기 등으로 할 수 있다.In the formula (3), R 7 is a hydrogen atom or a methyl group, 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, a decyl group, a dodecyl group, A hexadecyl group, an octadecyl group, an isooctadecyl group, a cyclopentyl group, a cyclohexyl group, etc. can be used.

상기 식 (3)으로 표시되는 화합물로서는, 아크릴산, 메타크릴산, 메틸아크릴레이트, 에틸아크릴레이트, 프로필아크릴레이트, 부틸아크릴레이트, 헥실아크릴레이트, 옥틸아크릴레이트, 데실아크릴레이트, 도데실아크릴레이트, 헥사데실아크릴레이트, 옥타데실아크릴레이트, 이소옥타데실아크릴레이트, 시클로펜틸아크릴레이트, 시클로헥실아크릴레이트, 메틸메타크릴레이트, 에틸메타크릴레이트, 프로필메타크릴레이트, 부틸메타크릴레이트, 헥실메타크릴레이트, 옥틸메타크릴레이트, 데실메타크릴레이트, 도데실메타크릴레이트, 헥사데실메타크릴레이트, 옥타데실메타크릴레이트, 이소옥타데실메타크릴레이트, 스테아릴메타크릴레이트, 시클로펜틸메타크릴레이트, 시클로헥실메타크릴레이트 등을 들 수 있다. 이들 중, 에틸아크릴레이트, 메틸메타크릴레이트 및 부틸아크릴레이트가 바람직하고, 메틸메타크릴레이트가 특히 바람직하다.Examples of the compound represented by the 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, 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 A methacrylate etc. are mentioned. Among these, ethyl acrylate, methyl methacrylate and butyl acrylate are preferable, and methyl methacrylate is particularly preferable.

상기 식 (4)에 있어서, R9는 수소 원자 또는 메틸기이고, R10 및 R11은 수소 원자, 또는 메틸기, 에틸기, 프로필기, 이소프로필기 등으로 할 수 있다. 또한, R10 및 R11은 동시에 수소 원자는 되지 않는다.In the 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. Further, R 10 and R 11 do not simultaneously become hydrogen atoms.

상기 식 (4)로 표시되는 화합물로서는, N-메틸아크릴아미드, N,N-디메틸아크릴아미드, N-에틸아크릴아미드, N,N-디에틸아크릴아미드, N-이소프로필아크릴아미드, N,N-디이소프로필아크릴아미드 등을 들 수 있다. 이들 중, N,N-디메틸아크릴아미드가 바람직하다.Examples of the compound represented by the formula (4) include N-methylacrylamide, N,N-dimethylacrylamide, N-ethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, N,N - Diisopropyl acrylamide, etc. are mentioned. Among these, N,N-dimethylacrylamide is preferable.

상기 성분 (B)가 구조 단위 (s-1)과, 구조 단위 (s-2), (s-3) 및 (s-4)에서 선택된 적어도 1종을 포함하는 공중합체인 경우, 구조 단위의 전량을 100질량%로 한 경우에, 구성 단위 (s-1)의 함유 비율은 방담성, 미끄럼성 및 대전 방지성의 관점에서 바람직하게는 10 내지 60질량%이다. 또한, 이 구성을 갖는 수지의 수 평균 분자량은 바람직하게는 10000 내지 100000이다.When the component (B) is a copolymer comprising a structural unit (s-1) and at least one selected from structural units (s-2), (s-3) and (s-4), the total amount of the structural unit is 100 mass%, the content rate of the structural unit (s-1) is preferably 10 to 60 mass% from the viewpoints of antifogging properties, sliding properties and antistatic properties. Moreover, the number average molecular weight of resin which has this structure becomes like this. Preferably it is 10000-100000.

상기 수 평균 분자량은 수계 GPC(겔 침투 크로마토그래피)를 사용하여, 공지된 방법에 의해 측정할 수 있다.The said number average molecular weight can be measured by a well-known method using aqueous|water-based GPC (gel permeation chromatography).

상기 성분 (B)로서 바람직한 공중합체는 이하에 나타내진다.The copolymer preferable as said component (B) is shown below.

(B-1) 상기 화합물 (m1-1)에서 유래하는 구조 단위와, 히드록시에틸메타크릴레이트에서 유래하는 구조 단위와, 메틸메타크릴레이트에서 유래하는 구조 단위를 포함하는 공중합체(B-1) a copolymer comprising a structural unit derived from the compound (m1-1), a structural unit derived from hydroxyethyl methacrylate, and a structural unit derived from methyl methacrylate

(B-2) 상기 화합물 (m1-1)에서 유래하는 구조 단위와, 히드록시에틸메타크릴레이트에서 유래하는 구조 단위와, 메틸메타크릴레이트에서 유래하는 구조 단위를 포함하는 공중합체(B-2) A copolymer comprising a structural unit derived from the compound (m1-1), a structural unit derived from hydroxyethyl methacrylate, and a structural unit derived from methyl methacrylate

(B-3) 상기 화합물 (m1-1)에서 유래하는 구조 단위와, 히드록시에틸메타크릴레이트에서 유래하는 구조 단위와, 메틸메타크릴레이트에서 유래하는 구조 단위를 포함하는 공중합체(B-3) A copolymer comprising a structural unit derived from the compound (m1-1), a structural unit derived from hydroxyethyl methacrylate, and a structural unit derived from methyl methacrylate

(B-4) 상기 화합물 (m1-2)에서 유래하는 구조 단위와, 히드록시에틸메타크릴레이트에서 유래하는 구조 단위와, 메틸메타크릴레이트에서 유래하는 구조 단위를 포함하는 공중합체(B-4) A copolymer comprising a structural unit derived from the compound (m1-2), a structural unit derived from hydroxyethyl methacrylate, and a structural unit derived from methyl methacrylate

(B-5) 상기 화합물 (m1-3)에서 유래하는 구조 단위와, 히드록시에틸아크릴레이트에서 유래하는 구조 단위와, 에틸아크릴레이트에서 유래하는 구조 단위를 포함하는 공중합체(B-5) A copolymer comprising a structural unit derived from the compound (m1-3), a structural unit derived from hydroxyethyl acrylate, and a structural unit derived from ethyl acrylate

(B-6) 상기 화합물 (m1-1)에서 유래하는 구조 단위와, 히드록시에틸메타크릴레이트에서 유래하는 구조 단위와, N,N-디메틸아크릴아미드에서 유래하는 구조 단위를 포함하는 공중합체(B-6) A copolymer comprising a structural unit derived from the compound (m1-1), a structural unit derived from hydroxyethyl methacrylate, and a structural unit derived from N,N-dimethylacrylamide

(B-7) 상기 화합물 (m1-1)에서 유래하는 구조 단위와, 히드록시에틸메타크릴레이트에서 유래하는 구조 단위와, 부틸아크릴레이트에서 유래하는 구조 단위를 포함하는 공중합체(B-7) A copolymer comprising a structural unit derived from the compound (m1-1), a structural unit derived from hydroxyethyl methacrylate, and a structural unit derived from butyl acrylate

(B-8) 메틸메타크릴레이트에서 유래하는 구조 단위와, 에틸아크릴레이트에서 유래하는 구조 단위와, 부틸아크릴레이트에서 유래하는 구조 단위와, 아크릴산에서 유래하는 구조 단위를 포함하는 공중합체(B-8) A copolymer comprising 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

상기 성분 (B)로서는 공지된 방법, 예를 들어 상기 식 (1)로 표시되는 화합물과, 상기 식 (2)로 표시되는 화합물, 상기 식 (3)으로 표시되는 화합물 및 상기 식 (4)로 표시되는 화합물에서 선택된 적어도 1종을 메탄올 등의 용매에 용해하고, 중합 개시제, 연쇄 이동제 등을 적절히 첨가한 후, 질소 분위기 하에서 라디칼 중합 반응을 행함으로써 합성된 것을 사용할 수 있다.As said component (B), a well-known method, for example, the compound represented by the said Formula (1), the compound represented by the said Formula (2), the compound represented by the said Formula (3), and the said Formula (4) What was synthesized by dissolving at least one selected from the indicated compounds in a solvent such as methanol, appropriately adding a polymerization initiator, a chain transfer agent, and the like, and performing a radical polymerization reaction in a nitrogen atmosphere can be used.

본 발명의 수지 시트용 개질제가 상기 성분 (B)를 함유하는 경우, 그의 함유 비율은 수지 시트용 개질제의 전체에 대하여 바람직하게는 35 내지 85질량%, 보다 바람직하게는 38 내지 65질량%이다.When the modifier for resin sheets of the present invention contains the component (B), the content thereof is preferably 35 to 85% by mass, more preferably 38 to 65% by mass relative to the entire modifier for resin sheets.

본 발명의 수지 시트용 개질제를 제조하는 경우, 상기 친수성 수지용의 제조 원료로서는 상기 성분 (B)의 수용액이 바람직하게 사용된다.When manufacturing the modifier for resin sheets of this invention, the aqueous solution of the said component (B) is used preferably as a manufacturing raw material for the said hydrophilic resin.

상기한 바와 같이, 친수성 수지는 수성 매체에 용해되지 않고, 그 중에서 분산되는 것이어도 된다. 이 경우, 라텍스, 에멀션 등을 사용할 수 있다.As described above, the hydrophilic resin may be dispersed in the aqueous medium without being dissolved. In this case, latex, emulsion, etc. can be used.

본 발명의 수지 시트용 개질제가 첨가제를 함유하는 경우, 이 첨가제로서는 활제, 대전 방지제, 산화 방지제, 자외선 흡수제, 난연제, 착색제, 이형제 등을 들 수 있다. 본 발명의 수지 시트용 개질제는 활제(이하, 「성분 (C)」라고 한다)를 함유하는 것이 바람직하다.When the modifier for resin sheets 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, a mold release agent, and the like. It is preferable that the modifier for resin sheets of this invention contains a lubricant (henceforth "component (C)").

상기 성분 (C)로서는, 유기 카르복실산, 유기 카르복실산염, 유기 카르복실산에스테르, 유기 카르복실산아미드, 폴리에틸렌 왁스, 실리콘 오일, 실리카 입자, 실리콘 수지 입자, 탈크 분말 등을 들 수 있다. 본 발명의 수지 시트용 개질제는 이들 성분의 1종만을 함유해도 되고, 2종 이상을 함유해도 된다. 본 발명에 있어서는, 유기 카르복실산염(이하, 「성분 (C1)」이라고 한다)이 특히 바람직하다.Examples of the component (C) include organic carboxylic acids, organic carboxylates, organic carboxylic acid esters, organic carboxylic acid amides, polyethylene wax, silicone oil, silica particles, silicone resin particles, and talc powder. The modifier for resin sheets of this invention may contain only 1 type of these components, and may contain 2 or more types. In the present invention, an organic carboxylate (hereinafter referred to as "component (C1)") is particularly preferable.

상기 성분 (C1)은 유기 카르복실산의 염이면 특별히 한정되지 않는다. 유기 카르복실산은 R-COOH(R은 히드록시기를 포함해도 되는 탄화수소기이다)로 표현되는 화합물이며, 예를 들어 포름산, 아세트산, 프로피온산, 부티르산, 발레르산, 카프로산, 소르브산, 에난트산, 카프릴산, 펠라르곤산, 카프르산, 운데실산, 운데실렌산, 라우르산, 트리데실산, 미리스트산, 펜타데실산, 팔미트산, 마르가르산, 스테아르산, 아라키드산, 헨이코실산, 베헨산, 트리코실산, 리그노세르산, 올레산, 리놀레산, 리놀렌산, 에루크산, 12-히드록시스테아르산, 리시놀레산 등을 들 수 있다. 이들 중, 얻어지는 표면 개질 수지 시트에 있어서의 미끄럼성의 관점에서, 탄소 원자수 14 내지 22의 지방족 카르복실산(히드록시기를 포함해도 된다)이 바람직하다. 또한, 염은 리튬염, 나트륨염, 칼륨염, 루비듐염, 세슘염 등의 1가의 알칼리 금속염이 바람직하고, 나트륨염 및 칼륨염이 특히 바람직하다.The component (C1) is not particularly limited as long as it is a salt of an organic carboxylic acid. Organic carboxylic acid is a compound represented by R-COOH (R is a hydrocarbon group which may contain a hydroxyl group), for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, sorbic acid, enantic acid, caprylic acid Acid, pelargonic acid, capric acid, undecylic acid, undecylenic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, henico and silicic acid, behenic acid, tricosylic acid, lignoceric acid, oleic acid, linoleic acid, linolenic acid, erucic acid, 12-hydroxystearic acid, and ricinoleic acid. Among these, from a viewpoint of the slipperiness in the surface modification resin sheet obtained, a C14-C22 aliphatic carboxylic acid (it may contain a hydroxyl group) is preferable. The salt is preferably a monovalent alkali metal salt such as a lithium salt, a sodium salt, a potassium salt, a rubidium salt or a cesium salt, and particularly preferably a sodium salt and a potassium salt.

본 발명의 수지 시트용 개질제는 성분 (A), 성분 (B) 및 성분 (C)를 함유하는 것이 바람직하다. 이 경우, 성분 (A)와 성분 (B) 및 성분 (C)의 함유 비율은, 수지 시트용 개질제(개질층 형성용 조성물)를 사용한 기재 수지 시트에 대한 접착성, 그리고 얻어지는 표면 개질 수지 시트에 있어서의 방담성, 미끄럼성 및 대전 방지성의 관점에서, 이들의 합계를 100질량%로 한 경우에 각각 바람직하게는 0.1 내지 15.0질량%, 35.0 내지 85.0질량% 및 15.0 내지 60.0질량%, 보다 바람직하게는 0.1 내지 10.0질량%, 38.0 내지 65.0질량% 및 30.0 내지 60.0질량%이다.It is preferable that the modifier for resin sheets of this invention contains a component (A), a component (B), and a component (C). In this case, the content ratio of component (A), component (B), and component (C) is determined by the adhesion to the base resin sheet using the modifier for resin sheet (composition for forming a modified layer), and the surface modified resin sheet obtained. From the viewpoint of anti-fogging properties, slipping properties and antistatic properties, when the total thereof is 100% by mass, preferably 0.1 to 15.0% by mass, 35.0 to 85.0% by mass and 15.0 to 60.0% by mass, more preferably is 0.1 to 10.0 mass%, 38.0 to 65.0 mass%, and 30.0 to 60.0 mass%.

본 발명의 수지 시트용 개질제는 기재 수지 시트의 표면에, 방담성, 미끄럼성 및 대전 방지성이 우수한 개질층을 갖는 표면 개질 수지 시트를 제조하는 원료이다. 바람직하게는, 성분 (A) 등이 액상 매체(물, 알코올 등에서 선택된 적어도 하나이며, 바람직하게는 물, 또는 물과 탄소 원자수 1 내지 3의 알코올의 혼합액)와 함께 포함되어, 기재 수지 시트에 대한 도포에 적합한 액상의 개질층 형성용 조성물이다. 이 액상 조성물에 있어서, 액상 매체의 함유 비율은 특별히 한정되지 않는다.The modifier for resin sheets of the present invention is a raw material for producing a surface-modified resin sheet having a modified layer excellent in antifogging properties, slip properties and antistatic properties on the surface of the base resin sheet. Preferably, the component (A) and the like are included together with a liquid medium (at least one selected from water, alcohol, etc., preferably water or a mixture of water and an alcohol having 1 to 3 carbon atoms) to form the base resin sheet. It is a liquid composition for forming a modified layer suitable for application to the skin. In this liquid composition, the content rate of a liquid medium is not specifically limited.

상기 기재 수지 시트에 액상의 개질층 형성용 조성물을 포함하는 수지 시트용 개질제를 도포하는 방법은 특별히 한정되지 않고, 공지된 방법을 사용할 수 있다. 예를 들어 스프레이 코트법, 그라비아 코트법, 에어 나이프 코트법, 바 코트법, 키스 코트법, 플로 코트법, 딥 코트법 등을 들 수 있다. 수지 시트용 개질제를 도포한 후, 통상, 도막의 건조가 행해진다. 건조 온도는 바람직하게는 60℃ 내지 120℃이다.A method of applying the modifier for a resin sheet containing a liquid composition for forming a modified layer to the base resin sheet is not particularly limited, and a known method may be used. For example, the spray coat method, the gravure coat method, the air knife coat method, the bar coat method, the kiss coat method, the flow coat method, the dip coat method etc. are mentioned. After apply|coating the modifier for resin sheets, drying of a coating film is performed normally. The drying temperature is preferably 60°C to 120°C.

본 발명에 있어서 수지 시트용 개질제를 도포하는 다른 기재 수지 시트로서는, 공지된 수지를 포함하는 것을 사용할 수 있다. 상기 기재 수지 시트는 바람직하게는 열가소성 수지 시트이며, 이 열가소성 수지는 예를 들어 1) 폴리스티렌, 스티렌·아크릴로니트릴 공중합체 등의 방향족 비닐 수지, 2) 폴리에틸렌테레프탈레이트 등의 폴리에스테르 수지, 3) 폴리락트산 등의 지방족 에스테르 수지, 4) 폴리염화비닐, 에틸렌·염화비닐 공중합체 등의 염화비닐계 수지, 5) 폴리메틸메타크릴레이트, 메틸메타크릴레이트·스티렌 공중합체 등의 아크릴계 수지, 6) 6-나일론, 6,6-나일론 등의 폴리아미드 수지, 7) 폴리카르보네이트 수지, 8) 폴리에틸렌, 폴리프로필렌 등의 폴리올레핀 수지 등을 들 수 있다. 이들 중, 폴리스티렌 등의 방향족 비닐 수지, 폴리에틸렌테레프탈레이트 등의 폴리에스테르 수지 및 폴리프로필렌 등의 폴리올레핀 수지가 바람직하다. 이들 열가소성 수지를 포함하는 시트는 비정질 시트, 비연신 시트, 동시 이축 연신 시트, 축차 이축 연신 시트 등 중 어느 것이어도 되고, 종래 공지된 시트 성형 수단으로 제조된 것을 사용할 수 있다. 또한, 상기 기재 수지 시트는 필요에 따라, 코로나 처리, 플라스마 처리, 프레임 처리, 산 또는 알칼리에 의한 약액 처리 등의 표면 처리가 실시된 것이어도 된다. 액상의 개질층 형성용 조성물을 포함하는 수지 시트용 개질제가 도포되는 표면의 JIS K 6768에 준하여 측정되는 습윤 장력은 특별히 제한은 없지만, 수지 시트용 개질제의 접착성의 관점에서 35mN/m 내지 70mN/m인 것이 바람직하다.As another base material resin sheet to which the modifier for resin sheets is apply|coated in this invention, the thing containing well-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, 2) a polyester resin such as polyethylene terephthalate, 3) Aliphatic ester resins such as polylactic acid, 4) Vinyl chloride resins such as polyvinyl chloride and ethylene/vinyl chloride copolymer, 5) Acrylic resins such as polymethyl methacrylate and methyl methacrylate/styrene copolymer, 6) polyamide resins, such as 6-nylon and 6,6-nylon, 7) polycarbonate resin, 8) polyolefin resin, such as polyethylene and polypropylene, etc. are mentioned. Among 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, or the like, and one manufactured by a conventionally known sheet forming means may be used. Moreover, the said base material resin sheet may be surface-treated, such as corona treatment, a plasma treatment, a flame|frame treatment, and chemical|medical solution treatment with acid or alkali as needed. The wetting tension measured according to JIS K 6768 on the surface to which the modifier for a resin sheet containing a liquid composition for forming a modified layer is applied is not particularly limited, but 35 mN/m to 70 mN/m from the viewpoint of the adhesiveness of the modifier for a resin sheet. It is preferable to be

상기 기재 수지 시트의 두께는 특별히 한정되지 않는다.The thickness of the said base material resin sheet is not specifically limited.

본 발명의 표면 개질 수지 시트는 기재 수지 시트에서 유래해서 수지를 포함하는 기층과, 해당 기층의 적어도 1면측에 배치된, 상기 본 발명의 수지 시트용 개질제를 포함하는 개질층을 구비한다. 바람직하게는, 액상의 개질층 형성용 조성물을 포함하는 수지 시트용 개질제가 기재 수지 시트의 적어도 1면측에 도포되어서 얻어진 것이며, 특히 상기 본 발명의 수지 시트용 개질제가 1면측당, 고형분 환산으로 바람직하게는 10 내지 200㎎/㎡, 보다 바람직하게는 30 내지 200㎎/㎡의 양으로 표면에 첨착된 수지 시트이다.The surface-modified resin sheet of the present invention includes a base layer containing a resin derived from the base resin sheet, and a modified layer containing the modifier for a resin sheet of the present invention, which is disposed on at least one side of the base layer. Preferably, a modifier for a resin sheet comprising a composition for forming a modified layer in a liquid form is obtained by coating at least one side of a base resin sheet, and in particular, the modifier for a resin sheet of the present invention is preferable in terms of solid content per side. It is preferably a resin sheet adhered to the surface in an amount of 10 to 200 mg/m 2 , more preferably 30 to 200 mg/m 2 .

본 발명의 표면 개질 수지 시트에 있어서, 개질층의 두께는 특별히 한정되지 않는다. 본 발명의 표면 개질 수지 시트가 양면에 개질층을 구비하는 경우, 각 개질층의 두께는 동일해도 되고, 상이해도 된다.In the surface-modified resin sheet of the present invention, the thickness of the modified layer is not particularly limited. When the surface modification resin sheet of this invention is equipped with a modification layer on both surfaces, the thickness of each modification layer may be same or different.

본 발명의 표면 개질 수지 시트는 개질층의 표면에, 필요에 따라 이형층을 구비할 수도 있다. 이형층은 실리콘 오일, 폴리옥시알킬렌 중합체 등을 포함하는 것으로 할 수 있다. 개질층 및 이형층을 순차 구비하는 표면 개질 수지 시트를 제조하는 방법으로서는, 기재 수지 시트의 표면에 개질층을 형성한 후, 이 개질층의 표면에 이형제 조성물을 도포하는 방법, 기재 수지 시트의 표면에, 이형제를 아울러 포함하는 수지 시트용 개질제를 도포하고, 그 후 이형제를 표면측으로 이동시키는 방법 등으로 할 수 있다. 본 발명의 표면 개질 수지 시트가 1면측에만 개질층을 구비하는 경우, 개질층이 없는 측에 이형층을 구비해도 된다.The surface-modified resin sheet of the present invention may include a release layer on the surface of the modified layer as needed. The release layer may contain silicone oil, polyoxyalkylene polymer, or the like. As a method for manufacturing a surface-modified resin sheet having a modified layer and a release layer sequentially, a method of forming a modified layer on the surface of a base resin sheet and then applying a release agent composition to the surface of the modified layer, the surface of the base resin sheet It can be set as the method etc. which apply|coat the modifier for resin sheets which also contains a mold release agent together, and move a mold release agent to the surface side after that. When the surface-modified resin sheet of the present invention includes a modified layer only on one side side, a release layer may be provided on the side without the modified layer.

본 발명의 표면 개질 수지 시트는 방담성이 우수하기 때문에, 이 시트를 통해서 반대측에 위치하는 물품의 시인성이 높고, 개질층에 있어서 미끄럼성이 우수하기 때문에 개질층이 물품과 접촉한 경우에 물품의 손상 또는 개질층의 파단이 없고, 개질층에 있어서 대전 방지성이 우수하기 때문에 티끌이나 먼지의 부착을 억제할 수 있다. 이러한 작용은 시트 뿐만 아니라, 이 시트를 가공해서 얻어진 성형품에 있어서도 얻을 수 있다.Since the surface-modified resin sheet of the present invention has excellent anti-fogging properties, the visibility of the article positioned on the opposite side through the sheet is high, and since the modified layer has excellent slidability, when the modified layer is in contact with the article, the article There is no damage or breakage of the modified layer, and since the modified layer has excellent antistatic properties, adhesion of dust and dirt can be suppressed. Such an action can be obtained not only in the sheet, but also in a molded article obtained by processing the sheet.

상기 성형품은 상기 본 발명의 표면 개질 수지 시트를 성형함으로써 제조할 수 있다. 성형 방법으로서는 진공 성형, 압공 성형 등을 들 수 있다. 또한, 성형품은 음료 및 식품용 용기의 덮개나 트레이, 전자 부품의 포장 용기 등에 이용할 수 있다.The molded article can be produced by molding the surface-modified resin sheet of the present invention. As a shaping|molding method, vacuum shaping|molding, air pressure shaping|molding, etc. are mentioned. In addition, the molded article can be used for a cover or tray of a container for beverages and food, a packaging container for electronic components, and the like.

[실시예][Example]

이하, 본 발명의 구성 및 효과를 보다 구체적으로 하기 위해서 실시예를 들지만, 본 발명은 이들 실시예에 한정되는 것은 아니다. 또한, 이하의 실시예 및 비교예에 있어서「%」 및 「부」는 질량 기준이다.Hereinafter, although an Example is given in order to make the structure and effect of this invention more concretely, this invention is not limited to these Examples. In addition, in the following examples and comparative examples, "%" and "part" are based on mass.

이하에 있어서, 처음에 액상 매체를 함유하는 수지 시트용 개질제(개질층 형성용 조성물)를 제조하고, 그 후 이 개질제를 기재 수지 시트에 도포하여 표면 개질 수지 시트를 제조한 예를 나타내지만, 본 발명은 액상 매체를 함유하지 않는 구성의 수지 시트용 개질제로 할 수 있는 것은 말할 필요도 없다.In the following, an example is shown in which a modifier for a resin sheet containing a liquid medium (composition for forming a modified layer) is first prepared, and then this modifier is applied to a base resin sheet to prepare a surface-modified resin sheet. Needless to say, the invention can be made as a modifier for a resin sheet having a structure that does not contain a liquid medium.

1. 시험 구분 1(수지 시트용 개질제의 원료)1. Test Category 1 (Raw material of modifier for resin sheet)

실시예 및 비교예에 사용한 원료를 나타낸다.The raw materials used for the Example and the comparative example are shown.

1-1. 원료 (A)1-1. Raw material (A)

본 발명에 관한 성분 (A)에 대응하는 원료는 이하와 같다.The raw material corresponding to the component (A) which concerns on this invention is as follows.

(A-1) 염화나트륨 분말(A-1) Sodium Chloride Powder

(A-2) 황산나트륨 분말(A-2) Sodium Sulfate Powder

(A-3) 염화칼륨 분말(A-3) Potassium Chloride Powder

(A-4) 염화리튬 분말(A-4) Lithium Chloride Powder

(a-1) 염화마그네슘 분말(a-1) Magnesium Chloride Powder

(a-2) 황산마그네슘 분말(a-2) Magnesium sulfate powder

(a-3) 탄산칼슘 분말(a-3) Calcium carbonate powder

1-2. 원료 (B)1-2. Raw material (B)

본 발명에 관한 성분 (B)에 대응하는 원료를 이하의 합성예 1 내지 8에 의해 얻었다.Raw materials corresponding to the component (B) according to the present invention were obtained by the following Synthesis Examples 1 to 8.

합성예 1(비닐 공중합체 (B-1)의 합성)Synthesis Example 1 (Synthesis of vinyl copolymer (B-1))

교반 장치 및 환류 장치를 구비하는 반응 용기에, 이소프로판올 300g, N,N-디메틸아미노에틸메타크릴레이트 65.9g(0.42몰), 히드록시에틸메타크릴레이트 45.1g(0.35몰), 메틸메타크릴레이트 90.3g(0.90몰) 및 아조비스이소부티로니트릴 1.2g을 투입하고, 이들을 혼합하고, 질소 가스 분위기 하에 80℃에서 3시간에 걸쳐서 라디칼 중합 반응을 행하였다. 이어서 얻어진 반응액에, 모노클로로아세트산나트륨 48.7g(0.42몰)과 물 629g을 포함하는 수용액을 10분에 걸쳐서 적하하고, 그 후 90℃까지 승온해서 이소프로판올 180g을 증류 제거했다. 얻어진 수용액을, 유도 결합 플라스마(ICP) 발광 분광 분석 장치로, 염화나트륨이 잔존하지 않게 될 때까지 이온 교환수 및 아세톤을 사용해서 정제했다. 이어서 수용액 중의 반응 생성물을 분석한 결과, 하기의 구조 단위를 소정의 비율로 포함하고, GPC에 의한 수 평균 분자량이 55000인 것을 알 수 있다. 이하, 이 친수성 아크릴 수지를 「비닐 공중합체 (B-1)」이라고 한다.In a reaction vessel equipped with a stirring device and a reflux device, 300 g of isopropanol, 65.9 g (0.42 mol) of N,N-dimethylaminoethyl methacrylate, 45.1 g (0.35 mol) of hydroxyethyl methacrylate, and 90.3 methyl methacrylate g (0.90 mol) and 1.2 g of azobisisobutyronitrile were added, these were mixed, and a radical polymerization reaction was performed at 80° C. for 3 hours in a nitrogen gas atmosphere. An aqueous solution containing 48.7 g (0.42 mol) of sodium 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. and 180 g of isopropanol was distilled off. The obtained aqueous solution was purified using an inductively coupled plasma (ICP) emission spectrometer using ion-exchanged water and acetone until sodium chloride no longer remained. Then, as a result of analyzing the reaction product in aqueous solution, it turns out that the following structural unit is included in a predetermined ratio, and the number average molecular weight by GPC is 55000. Hereinafter, this hydrophilic acrylic resin is called "vinyl copolymer (B-1)."

Figure pct00005
Figure pct00005

나중에 수지 시트용 개질제를 제조할 때에는, 이 비닐 공중합체 (B-1)을 25%의 농도로 함유하는 수용액(이하, 「수용액 (B-1x)」라고 한다)을 사용했다.Later, when manufacturing the modifier for resin sheets, an aqueous solution containing this vinyl copolymer (B-1) at a concentration of 25% (hereinafter referred to as "aqueous solution (B-1x)") was used.

합성예 2 내지 8(비닐 공중합체 (B-2) 내지 (B-8)의 합성)Synthesis Examples 2 to 8 (Synthesis of vinyl copolymers (B-2) to (B-8))

합성예 1과 마찬가지로 하여, 비닐 공중합체 (B-2) 내지 (B-8)을 합성했다.In the same manner as in Synthesis Example 1, vinyl copolymers (B-2) to (B-8) were synthesized.

비닐 공중합체 (B-2)는 하기의 구조 단위를 소정의 비율로 포함하고, GPC에 의한 수 평균 분자량이 25000인 공중합체이다.A vinyl copolymer (B-2) contains the following structural units in a predetermined ratio, and is a copolymer whose number average molecular weight by GPC is 25000.

Figure pct00006
Figure pct00006

비닐 공중합체 (B-3)은 하기의 구조 단위를 소정의 비율로 포함하고, GPC에 의한 수 평균 분자량이 80000인 공중합체이다.The vinyl copolymer (B-3) contains the following structural units in a predetermined ratio, and is a copolymer whose number average molecular weight by GPC is 80000.

Figure pct00007
Figure pct00007

비닐 공중합체 (B-4)는 하기의 구조 단위를 소정의 비율로 포함하고, GPC에 의한 수 평균 분자량이 50000인 공중합체이다.The vinyl copolymer (B-4) contains the following structural units in a predetermined ratio and is a copolymer having a number average molecular weight of 50000 by GPC.

Figure pct00008
Figure pct00008

비닐 공중합체 (B-5)는 하기의 구조 단위를 소정의 비율로 포함하고, GPC에 의한 수 평균 분자량이 50000인 공중합체이다.The vinyl copolymer (B-5) contains the following structural units in a predetermined ratio, and is a copolymer having a number average molecular weight of 50000 by GPC.

Figure pct00009
Figure pct00009

비닐 공중합체 (B-6)은 하기의 구조 단위를 소정의 비율로 포함하고, GPC에 의한 수 평균 분자량이 12000인 공중합체이다.The vinyl copolymer (B-6) contains the following structural units in a predetermined ratio, and is a copolymer whose number average molecular weight by GPC is 12000.

Figure pct00010
Figure pct00010

비닐 공중합체 (B-7)은 하기의 구조 단위를 소정의 비율로 포함하고, GPC에 의한 수 평균 분자량이 45000인 공중합체이다.The vinyl copolymer (B-7) contains the following structural units in a predetermined ratio, and is a copolymer whose number average molecular weight by GPC is 45000.

Figure pct00011
Figure pct00011

비닐 공중합체 (B-8)은 하기의 구조 단위를 소정의 비율로 포함하고, GPC에 의한 수 평균 분자량이 40000인 공중합체이다.The vinyl copolymer (B-8) contains the following structural units in a predetermined ratio, and is a copolymer having a number average molecular weight of 40000 by GPC.

Figure pct00012
Figure pct00012

그 후, 이들 비닐 공중합체 (B-2) 내지 (B-8)을 모두 25%의 농도로 함유하는 수용액(이하, 「수용액 (B-2x)」 내지 「수용액 (B-8x)」라고 한다)을 사용했다.Thereafter, an aqueous solution containing all of these vinyl copolymers (B-2) to (B-8) at a concentration of 25% (hereinafter referred to as “aqueous solution (B-2x)” to “aqueous solution (B-8x)” ) was used.

1-3. 원료 (C)1-3. Raw material (C)

본 발명에 관한 성분 (C)에 대응하는 원료는 이하와 같다.The raw material corresponding to the component (C) which concerns on this invention is as follows.

(C-1) 옥타데칸산나트륨 분말(C-1) Sodium Octadecanate Powder

(C-2) 옥타데센산나트륨 분말(C-2) sodium octadecenoate powder

(C-3) 헥사데센산나트륨 분말(C-3) Sodium Hexadecenate Powder

(C-4) 옥타데센산칼륨 분말(C-4) Potassium octadecenoate powder

(C-5) 옥타데칸산칼륨 분말(C-5) Potassium Octadecanate Powder

(C-6) 테트라데칸산나트륨 분말(C-6) Sodium Tetradecanoate Powder

(C-7) 도코센산칼륨 분말(C-7) Potassium docosenate powder

2. 시험 구분 2(수지 시트용 개질제의 조제)2. Test Category 2 (Preparation of modifier for resin sheet)

시험 구분 1로 나타낸 원료를 사용하여, 기재 수지 시트에 도포하기 위한 액상의 개질층 형성용 조성물을 포함하는 수지 시트용 개질제를 조제했다(표 1 참조). 또한, 이하의 실험에서는 액상의 개질층 형성용 조성물의 제조 원료로서 비닐 공중합체 (B-1)의 수용액 (B-1x)를 사용했지만, 상기한 바와 같이 수용액이 아니라, 액상 매체를 포함하지 않는 단리된 비닐 공중합체만을 사용한 수지 시트용 개질제로 하는 것도 가능하다.Using the raw material shown in Test Category 1, a modifier for a resin sheet containing a liquid composition for forming a modified layer for application to a base resin sheet was prepared (see Table 1). In addition, in the following experiments, an aqueous solution (B-1x) of the vinyl copolymer (B-1) was used as a raw material for preparing the composition for forming a liquid modified layer, but as described above, it is not an aqueous solution, but does not contain a liquid medium. It is also possible to set it as a modifier for resin sheets using only the isolated vinyl copolymer.

실시예 1-1Example 1-1

8.0부의 물과 4.4부의 수용액 (B-1x)와, 0.8부의 옥타데칸산나트륨 (C-1)과, 0.1부의 염화나트륨 (A-1)을 혼합하여, 고형분 15%의 수지 시트용 개질제 (E-1)을 조제했다. 이 수지 시트용 개질제 (E-1)에 있어서, 알칼리 금속 함유 무기 화합물/친수성 아크릴 수지/유기 카르복실산염의 고형분비(질량비)는 5/55/40이다.8.0 parts of water, 4.4 parts of an aqueous solution (B-1x), 0.8 parts of sodium octadecanoate (C-1), and 0.1 parts of sodium chloride (A-1) are mixed, and the modifier for a resin sheet having a solid content of 15% (E- 1) was prepared. In this modifier for resin sheets (E-1), the solid ratio (mass ratio) of the alkali metal-containing inorganic compound/hydrophilic acrylic resin/organic carboxylate is 5/55/40.

실시예 1-2 내지 1-13, 비교예 1-1 내지 1-6Examples 1-2 to 1-13, Comparative Examples 1-1 to 1-6

표 1의 원료를 사용하여, 실시예 1과 마찬가지로 하여 개질제 (E-2) 내지 (E-13) 및 (e-1) 내지 (e-6)을 조제했다.Using the raw materials of Table 1, modifiers (E-2) to (E-13) and (e-1) to (e-6) were prepared in the same manner as in Example 1.

Figure pct00013
Figure pct00013

3. 시험 구분 3(표면 개질 수지 시트의 제조 및 평가)3. Test Category 3 (Production and Evaluation of Surface Modified Resin Sheet)

시험 구분 2에서 제조한 수지 시트용 개질제를 사용해서 도공액을 조제하고, 그 후, 이 도공액 및 기재 수지 시트를 사용하여 표 2에 나타내는 표면 개질 수지 시트를 제조했다. 이하에 사용한 기재 수지 시트를 나타낸다.A coating solution was prepared using the modifier for resin sheets prepared in Test Category 2, and thereafter, the surface-modified resin sheets shown in Table 2 were prepared using this coating solution and the base resin sheet. The base resin sheet used below is shown.

(S-1) 폴리에스테르계 수지 시트(폴리에틸렌테레프탈레이트 수지 미결정 타입)(S-1) Polyester-based resin sheet (polyethylene terephthalate resin microcrystalline type)

(S-2) 폴리에스테르계 수지 시트(폴리에틸렌테레프탈레이트 수지 이축 연신 타입)(S-2) Polyester-based resin sheet (polyethylene terephthalate resin biaxially stretched type)

(S-3) 지방족 에스테르계 수지 시트(비연신 타입, 코로나 처리에 의해 JIS K 6768에 준하는 습윤 장력이 44mN/m인 것)(S-3) Aliphatic ester resin sheet (non-stretched type, having a wetting tension of 44 mN/m according to JIS K 6768 by corona treatment)

(S-4) 폴리스티렌계 수지 시트(비연신 타입, 코로나 처리에 의해 JIS K 6768에 준하는 습윤 장력이 44mN/m인 것)(S-4) Polystyrene-based resin sheet (non-stretched type, having a wetting tension of 44 mN/m according to JIS K 6768 by corona treatment)

(S-5) 폴리스티렌계 수지 시트(이축 연신 타입, 코로나 처리에 의해 JIS K 6768에 준하는 습윤 장력이 44mN/m인 것)(S-5) Polystyrene-based resin sheet (biaxial stretching type, having a wetting tension of 44 mN/m according to JIS K 6768 by corona treatment)

(S-6) 폴리올레핀계 수지 시트(폴리프로필렌, 비연신 타입, 코로나 처리에 의해 JIS K 6768에 준하는 습윤 장력이 44mN/m인 것)(S-6) Polyolefin resin sheet (polypropylene, non-stretched type, having a wetting tension of 44 mN/m according to JIS K 6768 by corona treatment)

(S-7) 폴리메타크릴산메틸 시트(비연신 타입, 코로나 처리에 의해 JIS K 6768에 준하는 습윤 장력이 44mN/m인 것)(S-7) polymethyl methacrylate sheet (non-stretched type, having a wetting tension of 44 mN/m according to JIS K 6768 by corona treatment)

실시예 2-1Example 2-1

실시예 1-1에서 제작한 고형분 15%의 수지 시트용 개질제 (E-1) 13.3g과, 물/이소프로필알코올=90/10(질량비)의 용매 86.7g을 혼합함으로써, 유효 농도 2%의 도공액을 조제했다.By mixing 13.3 g of the modifier (E-1) for a resin sheet 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), an effective concentration of 2% A coating liquid was prepared.

그 후, 폴리에스테르계 수지 시트 (S-1)에, 조제한 도공액을 바 코터로 도포했다(도포량: 5g/㎡). 그 후, 도막을 70℃에서 건조시켜, 절건 도포량이 100㎎/㎡인 개질층을 갖는 표면 개질 수지 시트 (P-1)을 제작했다.Thereafter, the prepared coating solution was applied to the polyester resin sheet (S-1) by a bar coater (application amount: 5 g/m 2 ). Then, the coating film was dried at 70 degreeC, and the surface-modified resin sheet (P-1) which has a modified layer whose absolute-dry application amount is 100 mg/m<2> was produced.

이어서, 얻어진 표면 개질 수지 시트 (P-1)에 대해서, 개질층 표면에 있어서의 방담성, 미끄럼성 및 대전 방지성의 평가를 행하였다. 그 결과를 표 2에 병기했다.Next, about the obtained surface-modified resin sheet (P-1), the antifogging property in the modified layer surface, sliding property, and antistatic property were evaluated. The result was written together in Table 2.

(1) 방담성(1) Anti-fogging properties

표면 개질 수지 시트를 직경 7㎝의 원형으로 잘라내고, 60℃의 뜨거운 물 100ml을 넣은 200ml 용량의 비이커에 개질층의 표면이 비이커의 내측이 되도록 씌우고, 5℃의 냉장고 안에 24시간 방치했다. 그 후, 표면 개질 수지 시트의 개질층의 표면에 있어서의 수적의 부착 정도를 관찰하여, 하기의 기준으로 방담성을 평가했다.The surface-modified resin sheet was cut into a circle with a diameter of 7 cm, placed in a 200 ml beaker containing 100 ml of hot water at 60 ° C., so that the surface of the modified layer was inside the beaker, and left in a refrigerator at 5 ° C. for 24 hours. Then, the adhesion degree of the water droplet in the surface of the modified layer of the surface modification resin sheet was observed, and the following reference|standard evaluated antifogging property.

<방담성의 평가 기준><Evaluation criteria for anti-fogging properties>

◎: 수적의 부착이 없고 투명했다(방담성이 우수하다)(double-circle): There was no adhesion of water droplets and it was transparent (excellent antifogging property)

○: 큰 수적의 부착이 있었지만 투명했다(방담성이 양호하다)(circle): There was adhesion of large water droplets, but it was transparent (good antifogging property)

△: 수적의 부착이 있어 약간 불투명했다(방담성이 떨어졌다)(triangle|delta): There was adhesion of water droplets, and it was slightly opaque (the antifogging property was inferior).

×: 작은 수적의 부착이 있어 불투명했다(방담성이 현저하게 떨어져 실용적이지 않다)x: There was adhesion of small water droplets and it was opaque (the antifogging property was remarkably inferior and it is not practical)

(2) 미끄럼성(2) slidability

JIS-K7125에 준거해서 개질층의 표면에 있어서의 운동 마찰 계수를 측정하고, 하기의 기준으로 미끄럼성을 평가했다.Based on JIS-K7125, the coefficient of kinetic friction on the surface of the modified layer was measured, and the sliding property was evaluated on the basis of the following criteria.

<미끄럼성의 평가 기준><Evaluation criteria for slippery property>

◎: 운동 마찰 계수가 0.25 미만이었다(double-circle): kinetic friction coefficient was less than 0.25

○: 운동 마찰 계수가 0.25 이상 0.30 미만이었다(circle): The coefficient of kinetic friction was 0.25 or more and less than 0.30.

△: 운동 마찰 계수가 0.30 이상 0.35 미만이었다(triangle|delta): kinetic friction coefficient was 0.30 or more and less than 0.35

×: 운동 마찰 계수가 0.35 이상이었다x: the coefficient of kinetic friction was 0.35 or more

(3) 대전 방지성(3) antistatic properties

표면 개질 수지 시트를 온도 20℃ 및 상대 습도 65%의 조건 하에 24시간 적재해서 조습한 후, 동일한 조건으로 표면 비저항(Ω)을 측정했다. 측정 기기는 시시도 덴키사제 표면 저항값 측정 장치(상품명: 메가레스타 HT-301)이다. 표면 저항값으로부터, 이하의 기준으로 대전 방지성을 평가했다.After loading the surface-modified resin sheet under the conditions of a temperature of 20°C and a relative humidity of 65% for 24 hours and controlling humidity, 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 Shishido Denki. From the surface resistance value, the following references|standards evaluated antistatic property.

<대전 방지성의 평가 기준><Evaluation criteria for antistatic properties>

◎: 표면 비저항이 5.0×108Ω 미만이었다(double-circle): surface resistivity was less than 5.0x10 8 ohms

○: 표면 비저항이 5.0×108Ω 이상 1.0×109Ω 미만이었다○: Surface resistivity was 5.0×10 8 Ω or more and less than 1.0×10 9 Ω

△: 표면 비저항이 1.0×109Ω 이상 5.0×109Ω 미만이었다△: Surface resistivity was 1.0×10 9 Ω or more and less than 5.0×10 9 Ω

×: 표면 비저항이 5.0×109Ω 이상이었다x: the surface resistivity was 5.0 x 10 9 Ω or more

실시예 2-2 내지 2-13 및 비교예 2-1 내지 2-6Examples 2-2 to 2-13 and Comparative Examples 2-1 to 2-6

수지 시트용 개질제 (E-1)을 대신하여, 수지 시트용 개질제 (E-2) 내지 (E-13) 및 (e-1) 내지 (e-6)을 사용한 것 이외에는, 실시예 2-1과 마찬가지로 하여 각 도공액을 조제했다. 이어서, 도공액을 표 2에 나타내는 기재 수지 시트의 표면에 도포하여, 개질층을 구비하는 표면 개질 수지 시트 (P-2) 내지 (P-13) 및 (p-1) 내지 (p-6)을 얻었다.Example 2-1 except that the modifiers for resin sheets (E-2) to (E-13) and (e-1) to (e-6) were used instead of the modifiers for resin sheets (E-1). Each coating solution was prepared in the same manner as described above. Next, the coating solution was applied to the surface of the base resin sheet shown in Table 2, and the surface-modified resin sheets (P-2) to (P-13) and (p-1) to (p-6) provided with a modified layer got

그 후, 실시예 2-1과 마찬가지로 하여 표면 개질 수지 시트의 평가를 행하였다. 그 결과를 표 2에 병기했다.Then, it carried out similarly to Example 2-1, and evaluated the surface modification resin sheet. The result was written together in Table 2.

Figure pct00014
Figure pct00014

4. 시험 구분 4(성형품의 제조)4. Test Category 4 (manufacturing of molded products)

시험 구분 3에서 제조한 표면 개질 수지 시트를 압공 성형에 제공하여, 개질층을 내표면으로 하는 각뿔대 모양의 성형품(개구부: 70㎜×70㎜, 저부: 60㎜×60㎜, 깊이: 30㎜)을 제조했다.The surface-modified resin sheet prepared in Test Category 3 was subjected to air pressure molding, and a truncated pyramid-shaped molded article having the modified layer as the inner surface (opening: 70 mm × 70 mm, bottom: 60 mm × 60 mm, depth: 30 mm) was manufactured

실시예 3-1Example 3-1

실시예 2-1에서 얻어진 표면 개질 수지 시트 (P-1)을 압공 성형기에 의해 가공하여, 각뿔대 모양의 성형품을 제작했다. 개질층의 박리 등의 문제는 보이지 않고, 외관성도 양호했다.The surface-modified resin sheet (P-1) obtained in Example 2-1 was processed by an air pressure molding machine to produce a truncated pyramidal molded article. Problems, such as peeling of a modified layer, were not seen, and the external appearance was also favorable.

실시예 3-2 내지 3-13Examples 3-2 to 3-13

표 2에 기재된 표면 개질 수지 시트를 사용하여, 실시예 3-1과 마찬가지로 하여 각뿔대 모양의 성형품을 제작했다. 어느 성형품에 있어서도, 개질층의 박리 등의 문제는 보이지 않고, 외관성도 양호했다.Using the surface modified resin sheet shown in Table 2, it carried out similarly to Example 3-1, and produced the truncated pyramid-shaped molded article. In any molded article, problems, such as peeling of a modified layer, were not seen, and the external appearance was also favorable.

본 발명의 수지 시트용 개질제를 기재 수지 시트의 표면에 도포함으로써, 방담성, 미끄럼성 및 대전 방지성이 우수한 개질층을 갖는 표면 개질 수지 시트를 제조할 수 있다. 본 발명의 표면 개질 수지 시트는 이 개질층의 표면에 있어서 방담성, 미끄럼성 및 대전 방지성이 우수하기 때문에, 이러한 표면 개질 수지 시트를 사용하여, 방담성, 미끄럼성 및 대전 방지성이 우수한 용기 등의 성형품을 효율적으로 제조할 수 있다. 그리고, 표면 개질 수지 시트 및 성형품은 식품 포장재나 식품 포장 용기, 전자 재료의 포장 용기 등 폭넓은 용도에 적합하다.By apply|coating the modifier for resin sheets of this invention to the surface of a base material resin sheet, the surface-modified resin sheet which has a modified layer excellent in antifogging property, sliding property, and antistatic property can be manufactured. Since the surface-modified resin sheet of the present invention has excellent anti-fogging properties, sliding properties and antistatic properties on the surface of the modified layer, a container having excellent anti-fogging properties, sliding properties and antistatic properties using such a surface-modified resin sheet It is possible to efficiently manufacture molded articles such as And the surface-modified resin sheet and molded article are suitable for a wide range of uses, such as a food packaging material, a food packaging container, and the packaging container of an electronic material.

Claims (13)

수지 시트의 표면 개질에 사용되는 개질제이며,
(A) 알칼리 금속 원소를 포함하는 무기 화합물
을 함유하는 것을 특징으로 하는 수지 시트용 개질제.It is a modifier used for surface modification of resin sheets,
(A) an inorganic compound containing an alkali metal element
A modifier for a resin sheet, comprising: 제1항에 있어서, 상기 성분 (A)에 포함되는 상기 알칼리 금속 원소가 리튬, 나트륨 및 칼륨에서 선택된 적어도 하나인 수지 시트용 개질제.The modifier for a resin sheet according to claim 1, wherein the alkali metal element contained in the component (A) is at least one selected from lithium, sodium and potassium. 제1항 또는 제2항에 있어서, 추가로,
(B) 친수성 아크릴 수지
를 함유하는 수지 시트용 개질제.3. The method of claim 1 or 2, further comprising:
(B) hydrophilic acrylic resin
A modifier for a resin sheet containing 제3항에 있어서, 상기 성분 (B)가, 하기 식 (1)로 표시되는 화합물에서 유래하는 구조 단위를 포함하는 중합체인 수지 시트용 개질제.
Figure pct00015

(식 중, R1은 수소 원자 또는 메틸기이고, R2는 탄소 원자수 1 내지 4의 2가의 탄화수소기이고, R3 및 R4는 서로 동일하거나 또는 상이한, 탄소 원자수 1 내지 4의 탄화수소기이다.)The modifier for resin sheets according to claim 3, wherein the component (B) is a polymer containing a structural unit derived from a compound represented by the following formula (1).
Figure pct00015

(Wherein, 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, a hydrocarbon group having 1 to 4 carbon atoms. am.) 제4항에 있어서, 상기 성분 (B)가 추가로, 하기 식 (2)로 표시되는 화합물에서 유래하는 구조 단위, 하기 식 (3)으로 표시되는 화합물에서 유래하는 구조 단위, 및 하기 식 (4)로 표시되는 화합물에서 유래하는 구조 단위에서 선택된 적어도 1종을 포함하는 수지 시트용 개질제.
Figure pct00016

(식 중, R5는 수소 원자 또는 메틸기이고, R6은 히드록시기를 1개 갖는 탄소 원자수 1 내지 4의 탄화수소기, 또는 히드록시기를 2개 갖는 탄소 원자수 2 내지 4의 탄화수소기이다.)
Figure pct00017

(식 중, R7은 수소 원자 또는 메틸기이고, R8은 수소 원자, 또는 탄소 원자수 1 내지 18의 탄화수소기이다.)
Figure pct00018

(식 중, R9는 수소 원자 또는 메틸기이고, R10 및 R11은 서로 동일하거나 혹은 상이한, 수소 원자, 또는 탄소 원자수 1 내지 3의 탄화수소기이다. 단, R10 및 R11의 양쪽이 수소 원자인 것을 제외한다.)The component (B) according to claim 4, further comprising 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 structural unit derived from a compound represented by the following formula (3), and the following formula (4) ) A modifier for a resin sheet comprising at least one selected from the group consisting of structural units derived from a compound represented by
Figure pct00016

(Wherein, R 5 is a hydrogen atom or a methyl group, and R 6 is a hydrocarbon group having 1 to 4 carbon atoms having one hydroxyl group, or a hydrocarbon group having 2 to 4 carbon atoms having two hydroxyl groups.)
Figure pct00017

(Wherein, 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.)
Figure pct00018

(Wherein, R 9 is a hydrogen atom or a methyl group, and R 10 and R 11 are the same or different from each other, a hydrogen atom, or a hydrocarbon group having 1 to 3 carbon atoms. However, both R 10 and R 11 are Except for hydrogen atoms.) 제3항 내지 제5항 중 어느 한 항에 있어서, 상기 성분 (B)의 수 평균 분자량이 10000 내지 100000인 수지 시트용 개질제.The modifier for resin sheets according to any one of claims 3 to 5, wherein the number average molecular weight of the component (B) is 10000 to 100000. 제1항 내지 제6항 중 어느 한 항에 있어서, 추가로,
(C) 활제
를 함유하는 수지 시트용 개질제.7. The method according to any one of claims 1 to 6, further comprising:
(C) lubricant
A modifier for a resin sheet containing 제7항에 있어서, 상기 활제 (C)가 유기 카르복실산염을 포함하는 수지 시트용 개질제.The modifier for a resin sheet according to claim 7, wherein the lubricant (C) contains an organic carboxylate. 제8항에 있어서, 상기 유기 카르복실산염이, 탄화수소기의 탄소 원자수가 14 내지 22인 지방족 카르복실산의 알칼리 금속염인 수지 시트용 개질제.The modifier for resin sheets according to claim 8, wherein the organic carboxylate is an alkali metal salt of an aliphatic carboxylic acid having 14 to 22 carbon atoms in the hydrocarbon group. 제7항 내지 제9항 중 어느 한 항에 있어서, 상기 성분 (B) 및 상기 성분 (C)를 함유하고, 상기 성분 (A), 상기 성분 (B) 및 상기 성분 (C)의 함유 비율이, 이들의 합계를 100질량%로 한 경우에, 각각 0.1 내지 15.0질량%, 35.0 내지 85.0질량% 및 15.0 내지 60.0질량%인 수지 시트용 개질제.The component (B) and the component (C) according to any one of claims 7 to 9, wherein the content ratio of the component (A), the component (B) and the component (C) is , When these sum total is 100 mass %, it is 0.1-15.0 mass %, 35.0-85.0 mass %, and 15.0-60.0 mass %, respectively, The modifier for resin sheets. 수지를 포함하는 기층과, 해당 기층의 적어도 1면측에 배치된, 제1항 내지 제10항 중 어느 한 항에 기재된 수지 시트용 개질제를 포함하는 개질층을 구비하는 것을 특징으로 하는 표면 개질 수지 시트.A surface-modified resin sheet comprising: a base layer comprising a resin; and a modified layer comprising the modifier for a resin sheet according to any one of claims 1 to 10, arranged on at least one side of the base layer. . 제11항에 있어서, 상기 기층에 포함되는 상기 수지가 폴리에스테르 수지, 방향족 비닐 수지 및 올레핀 수지에서 선택된 적어도 1종인 표면 개질 수지 시트.The surface-modified resin sheet according to claim 11, wherein the resin included in the base layer is at least one selected from a polyester resin, an aromatic vinyl resin, and an olefin resin. 제11항 또는 제12항에 기재된 표면 개질 수지 시트를 성형 가공에 제공하는 것을 특징으로 하는 성형품의 제조 방법.A method for producing a molded article, wherein the surface-modified resin sheet according to claim 11 or 12 is subjected to a molding process.
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