KR20090016125A - Intermediate film for laminated glass and a method of manufacturing the same - Google Patents

Intermediate film for laminated glass and a method of manufacturing the same Download PDF

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KR20090016125A
KR20090016125A KR1020070080538A KR20070080538A KR20090016125A KR 20090016125 A KR20090016125 A KR 20090016125A KR 1020070080538 A KR1020070080538 A KR 1020070080538A KR 20070080538 A KR20070080538 A KR 20070080538A KR 20090016125 A KR20090016125 A KR 20090016125A
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South Korea
Prior art keywords
sheet
laminated glass
interlayer film
embossed
manufacturing
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KR1020070080538A
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Korean (ko)
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KR100912497B1 (en
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김연수
지성대
유상현
한대만
성명석
송헌일
김용민
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웅진케미칼 주식회사
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Priority to KR1020070080538A priority Critical patent/KR100912497B1/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07Flat, e.g. panels
    • B29C48/08Flat, e.g. panels flexible, e.g. films
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10559Shape of the cross-section
    • B32B17/10568Shape of the cross-section varying in thickness
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10605Type of plasticiser
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10715Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyether
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10724Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyamide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10743Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing acrylate (co)polymers or salts thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10752Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polycarbonate
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10779Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyester
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10788Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing ethylene vinylacetate

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Thermal Sciences (AREA)
  • Joining Of Glass To Other Materials (AREA)

Abstract

A manufacturing method of an intermediate layer for stacking glass is provided to simplify a process by excluding adhesion and coating steps, to transfer embossment accurately, to penetrate an embossment roll excellently and to form easily concavo-convex. A manufacturing method of an intermediate layer for stacking glass comprises steps of: (S100) manufacturing sheet by extruding raw material; (S200) heating-up the manufactured sheet before an embossment imprint; and (S300) forming concavo-convex at a surface part of the heated sheet. The raw material is selected from a group consisting of TPVC, acryl, polyester, olefin, butyral-based, polycarbonate, polyimide and polyamide resin.

Description

적층유리용 중간막 및 이의 제조방법{Intermediate Film for Laminated Glass and a Method of manufacturing the same}Interlayer film for laminated glass and a method of manufacturing the same

본 발명은 적층유리용 중간막 및 이의 제조방법에 관한 것으로, 구체적으로는 양각의 전사가 용이하고, 뱅크 발생이 없고, 잔류 왜곡 및 가열수축률이 낮으며, 공정의 단순화가 제공되는 적층유리용 중간막 및 이의 제조방법에 관한 것이다.The present invention relates to an interlayer film for laminated glass and a method for manufacturing the same, and specifically, an interlayer film for laminated glass that is easy to transfer embossed, has no banks, has low residual distortion and heat shrinkage, and provides a simplified process. It relates to a manufacturing method thereof.

적층유리는 2장의 투명 판유리의 사이에 가소화 폴리비닐 부티랄 수지 등으로 되는 접착성 중간막이 협착 되어 제조되는데, 강도가 커서 파손되기 어렵고, 파손되더라도 파편이 비산하지 않는 안전한 유리재로서, 종래부터 자동차나 항공기 등의 수송용 기기 또는 건축물 등의 창문 유리에 폭넓게 사용되어 왔다. Laminated glass is manufactured by squeezing an adhesive interlayer made of plasticized polyvinyl butyral resin between two sheets of transparent glass, and is a safe glass material that is hard to break due to its high strength and does not scatter fragments even if broken. Background Art [0002] It has been widely used for window glass in transportation equipment such as automobiles and aircrafts or in buildings.

따라서, 적층유리에 사용되는 중간막은 보존 시에 중간막 사이가 합착되는 현상, 소위 블로킹(Blocking) 현상이 나타나지 않고, 유리 사이에 중간막의 적층이 용이하도록 하고, 적층유리의 예비 압착 공정에서 탈기가 양호하게 이루어지도록 해야 한다. 이러한 조건을 만족시키기 위해 중간막으로 일반적으로 양각 시트(Emboss sheet)라고 불리는 수지막이 사용되며, 상기 양각 시트는 수지막의 양면 또는 편면에 다수의 양각을 부여시킴으로서 형성된다.Therefore, the interlayer film used for the laminated glass does not exhibit the phenomenon of bonding between the interlayer films during storage, so-called blocking phenomenon, and facilitates lamination of the interlayer film between the glasses, and good degassing in the preliminary pressing process of the laminated glass. It should be done. In order to satisfy these conditions, a resin film commonly referred to as an emboss sheet is used as the interlayer film, and the embossed sheet is formed by giving a plurality of embossments to both surfaces or one side of the resin film.

이에 일본 특허공개 제1986-61835호에서는 압출되어 제조된 시트에 연속적으로 요철을 부여시킴에 있어, 1.2R + T ≤145의 공식을 만족시키며 요철을 전사시킴이 제안되었다. 상기 공식 중, R은 2층 시트의 표면 거칠기(㎛)이고, T는 온도이다.  In Japanese Patent Application Laid-Open No. 1986-61835, it is proposed to transfer unevenness while satisfying the formula of 1.2R + T? 145 in order to continuously give unevenness to an extruded sheet. In said formula, R is the surface roughness (micrometer) of a two-layer sheet, T is temperature.

그러나, 상기 기술에 있어서, 시트에 온도가 너무 높게 부여될 경우, 시트가 너무 부드러워져 양각 롤(Emboss roll)로 압력을 가하면 시트가 폭 방향으로 넓어져 충분한 압력을 가할 수 없게 되어 양각 전사율이 떨어지게 되며, 시트가 양각 롤에 침투하지 못하고 침투 직전에 뱅크(Bank;퇴적물)가 발생하여 시트가 안정하게 연속적으로 성형되지 못하게 된다. 게다가, 시트 반송을 위한 장력이 작으면 막이 떨어지고, 경우에 따라서는 막 갈라짐 현상이 발생될 수 있으므로 이 또한 연속적으로 성형되지 않게 된다. 한편, 시트에 온도가 너무 낮게 부여될 경우, 시트의 유연성이 부족하여 압력을 가해도 양각 전사가 어렵게 된다. However, in the above technique, when the temperature is imparted to the sheet too high, the sheet becomes so soft that when the pressure is applied to the emboss roll, the sheet widens in the width direction so that sufficient pressure cannot be applied and the embossed transfer rate is increased. As the sheet does not penetrate the embossed roll, a bank (bank) is generated immediately before the penetration, so that the sheet cannot be stably formed continuously. In addition, if the tension for conveying the sheet is small, the film may fall, and in some cases, a film cracking phenomenon may occur, which is also not continuously formed. On the other hand, when the temperature is too low, the embossed transfer becomes difficult even if pressure is applied due to the lack of flexibility of the sheet.

상기 발명의 개선으로 일본 특허발명 제1991-284935호에서는 시트 표면과 중심부의 온도차를 두어 표면의 양각 전사율을 향상시키고, 뱅크의 발생이나 잔류 왜곡 현상이 개선됨이 제안되었다. 그러나, 중심부와 시트 표면의 온도의 차이가 3 내지 7 ℃ 정도의 협소하게 제한된 온도 범위를 지녀 시트의 표면과 중심부의 온도 차이가 크지 않아, 뱅크 발생이나 잔류 왜곡 현상을 충분히 방지 할 수 없게 된다.As a further improvement of the invention, Japanese Patent Invention No. 1991-284935 proposes to improve the embossed transfer rate of the surface by providing a temperature difference between the surface of the sheet and the center, and to improve the occurrence of banks or residual distortion. However, since the temperature difference between the center and the sheet surface has a narrowly limited temperature range of about 3 to 7 ° C., the temperature difference between the surface of the sheet and the center is not large, so that bank generation or residual distortion cannot be sufficiently prevented.

따라서, 상기 단점을 해결하고자 일본 특허공개 제1998-138339호에서 개선된 방법이 제안되었다. 이에 대한 제조 공정도를 도 1에 나타내었다.Therefore, an improved method has been proposed in Japanese Patent Laid-Open No. 1998-138339 to solve the above disadvantage. A manufacturing process diagram thereof is shown in FIG. 1.

도 1은 기존의 적층유리용 중간막의 제조 장치 단면도이다.1 is a cross-sectional view of a manufacturing apparatus of a conventional interlayer film for laminated glass.

도 1을 참조하여 설명하면, 용융조 1 및 3을 통과하여 동일하게 제조된 열가소성 시트 11 및 13 사이에 용융조 2를 통과한 또다른 열가소성 시트 12 가 양각롤 9 에서 적층되어 이루어지는데, 시트 12 에 적용되는 온도는 시트 11 및 13 보다 10 내지 50 ℃ 정도 낮은 온도가 적용되고, 이후 압력을 가해 시트 11 및 13 에 양각롤 9 를 통해 양각을 전사시키며 적층됨을 특징으로 한 적층유리용 중간막이 제안되었다.Referring to FIG. 1, another thermoplastic sheet 12 passing through the melting tank 2 between the thermoplastic sheets 11 and 13 manufactured in the same manner through the melting tanks 1 and 3 is laminated on the relief roll 9. The temperature applied to the laminated glass 10 ~ 50 ℃ lower than the temperature is applied to the sheet 11 and 13, and then applied to the sheet 11 and 13 by transferring the embossed through the embossing roll 9 to the sheets 11 and 13 is proposed an interlayer film for laminated glass It became.

그러나, 상기 기술은 공정이 복잡하고, 시트 11 및 13과 시트 12에 부여되는 온도를 제어하기 어려우며, 이에 따라 시트 11 및 13과 시트 12의 적층이 어렵고, 적층되더라도 박리가 일어나기 쉬우며, 적층유리에 적용 시 유리의 투과율이 떨어지는 문제점이 있다.However, the above technique is complicated in the process, and it is difficult to control the temperature applied to the sheets 11 and 13 and the sheet 12, and thus, the lamination of the sheets 11 and 13 and the sheet 12 is difficult, and even when laminated, the peeling occurs easily, and the laminated glass When applied to there is a problem that the transmittance of the glass falls.

상기와 같은 문제점을 해결하기 위하여 본 발명의 목적은 적층유리용 중간막의 제조공정에 있어서, 두 형태의 시트가 아닌 한 형태로 시트를 형성시키고, 열가소성 시트가 양각 롤에 침투하기 직전에 열을 부여하여 점착 및 코팅 단계를 배제시킴으로서 공정의 단순화와 더불어 양각이 정확하게 전사되도록 하여 양각 롤의 침투가 양호하여 요철의 형성이 용이한 적층유리용 중간막 및 이의 제조방법을 제공하는 데 있다. In order to solve the above problems, an object of the present invention in the manufacturing process of the interlayer film for laminated glass, the sheet is formed in one form other than the two forms of the sheet, the heat is applied immediately before the thermoplastic sheet penetrates the embossing roll It is to provide an interlayer film for laminated glass and a method of manufacturing the same by simplification of the process by eliminating the adhesion and coating step so that the embossing is accurately transferred to the penetration of the embossed roll to facilitate the formation of irregularities.

또한, 본 발명의 다른 목적은 열가소성 시트가 양각 롤에 침투하기 직전에 열을 부여할 때, 시트의 표면을 가열하여 시트 내부인 중심부와 온도 차이를 두어 표면에 양면 또는 편면에 양각의 적용이 자유롭고, 뱅크 발생이 없으며, 잔류 왜곡 및 가열 수축률이 낮은 적층유리용 중간막 및 이의 제조방법을 제공하는 데 있다. In addition, another object of the present invention is that when the thermoplastic sheet is given heat just before the penetration into the embossed roll, the surface of the sheet is heated to leave a temperature difference with the center of the inside of the sheet so that embossing is freely applied to both surfaces or one side on the surface. The present invention provides an interlayer film for laminated glass having no banking, low residual distortion and low heat shrinkage, and a method of manufacturing the same.

상기 목적을 달성하기 위해 본 발명은 적층유리용 중간막에 있어서, 원료가 압출되어 이루어진 시트를 양각 전사 직전에 표면부와 중심부에 온도차를 두고 가열시켜, 시트의 표면부가 양각되어 이루어짐을 특징으로 한 적층유리용 중간막을 제공한다.In order to achieve the above object, the present invention is laminated in the interlayer film for laminated glass, the raw material is extruded by heating a sheet having a temperature difference between the surface portion and the center just before embossed transfer, the surface portion of the sheet is embossed laminated Provided is an interlayer film for glass.

또한, 본 발명은 상기 원료가 염화비닐계, 아크릴계, 폴리에스테르계, 올레핀계, 부티랄계, 폴리카보네이트계, 폴리이미드계 및 폴리아미드계 수지가 포함되어 이루어진 군에서 1 이상 선택되어 포함됨을 특징으로 하는 적층유리용 중간막을 제공한다.In addition, the present invention is characterized in that the raw material is selected from one or more selected from the group consisting of vinyl chloride, acrylic, polyester, olefin, butyral, polycarbonate, polyimide and polyamide resin. Provided is an interlayer film for laminated glass.

또한, 본 발명은 상기 원료가 부티랄계 수지로 이루어진 경우, 가소제가 첨가되되, 트리에틸렌 글리콜-2-에틸부틸레이트, 테트라에틸렌 글리콜-2-에틸 부틸레이트 및 g-부틸 지그 리콜 아디페이트가 포함되어 이루어진 군에서 1 이상 선택되어 가소화됨을 특징으로 하는 적층유리용 중간막을 제공한다.In addition, the present invention, when the raw material is made of a butyral resin, a plasticizer is added, triethylene glycol-2-ethyl butyrate, tetraethylene glycol-2-ethyl butyrate and g- butyl zigcol adipate is included Provided is an interlayer film for laminated glass, characterized in that at least one selected from the group consisting of plasticized.

또한, 본 발명은 상기 시트의 두께가 0.1 내지 3.0 mm 이고, 신장율이 1.0 내지 3.0 임을 특징으로 하는 적층유리용 중간막을 제공한다.In addition, the present invention provides an interlayer film for laminated glass, characterized in that the thickness of the sheet is 0.1 to 3.0 mm, elongation is 1.0 to 3.0.

또한, 본 발명은 상기 표면부의 온도가 중심부의 온도 보다 5 내지 60 ℃ 높게 가열됨을 특징으로 하는 적층유리용 중간막을 제공한다.In addition, the present invention provides an interlayer film for laminated glass, characterized in that the temperature of the surface portion is heated to 5 to 60 ℃ higher than the temperature of the center portion.

또한, 본 발명은 적층유리용 중간막의 제조방법에 있어서, 원료가 압출되어 이루어지는 시트 제조 단계;상기 제조된 시트가 표면부와 중심부에 온도차를 두어 양각 전사 직전에 가열되는 가열 단계; 및 상기 가열된 시트의 표면부에 요철이 형성되는 양각 전사 단계가 연속적으로 이루어짐을 특징으로 하는 적층유리용 중간막의 제조방법을 제공한다.In addition, the present invention is a method for producing an interlayer film for laminated glass, the raw material is a sheet manufacturing step is extruded; a heating step of heating the immediately before the embossed transfer by placing a temperature difference in the surface portion and the center portion; And it provides a method for producing an interlayer film for laminated glass, characterized in that the embossing transfer step of forming the irregularities on the surface of the heated sheet is made continuously.

또한, 본 발명은 상기 시트 제조 단계에 있어서, 상기 원료가 염화비닐계, 아크릴계, 폴리에스테르계, 올레핀계, 부티랄계, 폴리카보네이트계, 폴리이미드계 및 폴리아미드계 수지가 포함되어 이루어진 군에서 1 이상 선택되어 이루어짐을 특징으로 하는 적층유리용 중간막의 제조방법을 제공한다.In addition, the present invention in the sheet manufacturing step, the raw material is a vinyl chloride-based, acrylic, polyester-based, olefin-based, butyral-based, polycarbonate-based, polyimide-based and polyamide-based resin group 1 It provides a method for producing an interlayer film for laminated glass, characterized in that the selection is made above.

또한, 본 발명은 상기 원료가 부티랄계 수지로 이루어진 경우, 가소제가 첨가되되, 트리에틸렌 글리콜-2-에틸부틸레이트, 테트라에틸렌 글리콜-2-에틸 부틸레이트 및 g-부틸 지그 리콜 아디페이트가 포함되어 이루어진 군에서 1 이상 선택되어 가소화됨을 특징으로 하는 적층유리용 중간막의 제조방법을 제공한다.In addition, the present invention, when the raw material is made of a butyral resin, a plasticizer is added, triethylene glycol-2-ethyl butyrate, tetraethylene glycol-2-ethyl butyrate and g- butyl zigcol adipate is included Provided is a method for producing an interlayer film for laminated glass, characterized in that the plasticized by selecting at least one from the group consisting of.

또한, 본 발명은 상기 시트의 두께가 0.1 내지 3.0 mm 이고, 신장율이 1.0 내지 3.0 임을 특징으로 하는 적층유리용 중간막의 제조방법을 제공한다.In addition, the present invention provides a method for producing an interlayer film for laminated glass, characterized in that the thickness of the sheet is 0.1 to 3.0 mm, the elongation is 1.0 to 3.0.

또한, 본 발명은 상기 가열 단계에 있어서, 표면부의 온도가 중심부의 온도 보다 5 내지 60 ℃ 높게 가열됨을 특징으로 하는 적층유리용 중간막의 제조방법을 제공한다.In addition, the present invention provides a method for producing an interlayer film for laminated glass, in the heating step, the temperature of the surface portion is heated to 5 to 60 ℃ higher than the temperature of the central portion.

또한, 본 발명은 상기 가열 단계에 있어서, 가열 장치가 발열판이나 대기압 플라즈마가 이용되어 가열됨을 특징으로 하는 적층유리용 중간막의 제조방법을 제공한다.In addition, the present invention provides a method for producing an interlayer film for laminated glass, in the heating step, the heating device is heated using a heating plate or atmospheric pressure plasma.

또한, 본 발명은 상기 양각 전사 단계에 있어서, 양각 전사가 시트의 상하 양면에 동시에 부여되거나 구별된 공정으로 2단으로 진행됨을 특징으로 하는 적층유리용 중간막의 제조방법을 제공한다.In addition, the present invention provides a method for producing an interlayer film for laminated glass, characterized in that in the embossed transfer step, embossed transfer proceeds in two stages at the same time to the upper and lower sides of the sheet or in a distinct process.

또한, 본 발명은 상기 양각 전사 단계에 있어서, 시트에 양각 전사 방식이 한 쌍의 양각 롤이나 금속 벨트가 이용되어 양각이 전사됨을 특징으로 하는 적층유리용 중간막의 제조방법을 제공한다.The present invention also provides a method for producing an interlayer film for laminated glass, wherein in the embossed transfer step, the embossed transfer method is used on the sheet by using a pair of embossed rolls or metal belts.

또한, 본 발명은 상기 금속 벨트가 벨트의 양단을 용접하여 접합하여 이루어진 루프 상의 것임을 특징으로 하는 적층유리용 중간막의 제조방법을 제공한다.In addition, the present invention provides a method for producing an interlayer film for laminated glass, characterized in that the metal belt is on a loop formed by welding both ends of the belt.

또한, 본 발명은 상기 양각 롤 또는 금속 벨트에 양각 부여 방식이 조각, 부식 또는 샌드 블라스트 방식으로 양각이 부여된 후, 표면에 도금, 세라믹, 실리콘 코트 또는 테프론 코트 처리가 행해져 이루어짐을 특징으로 하는 적층유리용 중간막의 제조방법을 제공한다.In addition, the present invention is the embossed roll or the metal belt is embossed, the embossing method is engraved, corrosion or sandblasted after embossing, the surface is plated, ceramic, silicon coat or Teflon coat is carried out lamination, characterized in that made Provided is a method for producing an interlayer film for glass.

또한, 본 발명은 상기 양각 전사 단계에 있어서, 양각 전사 시에 온도 제어가 가능한 것을 특징으로 하는 적층유리용 중간막의 제조방법을 제공한다.In addition, the present invention provides a method for producing an interlayer film for laminated glass, characterized in that in the embossed transfer step, temperature control at the time of embossed transfer.

또한, 본 발명은 상기 양각 전사 단계에 있어서, 양각 롤의 압착 압력이 10 내지 100 kg/cm 인 것을 특징으로 하는 적층유리용 중간막의 제조방법을 제공한다.In addition, the present invention provides a method for producing an interlayer film for laminated glass, in the embossed transfer step, the pressing pressure of the embossed roll is 10 to 100 kg / cm.

또한, 본 발명은 상기 원료로서 부티랄화 65 mol%, 중합도 1,700의 폴리비닐 부티랄 100 중량부에 가소제로 트리에틸렌 글리콜-2-에틸 부틸레이트 40 중량부를 첨가하여 혼련시킨 폴리비닐 부티랄 수지를 용융조 에 투입하여 두께가 1.0 mm 되도록 압출하여 시트를 제조한 후, 냉각하여 온도 조절 롤로 시트 이동 시 신장율 1.3 이 되도록 하여 시트를 완성시킨 후, 상기 제조된 시트에 발열판을 이용하여 시트의 표면부에 온도 100 ℃ 및 중심부에 60 ℃ 가 되도록 가열 단계를 진행시키고, 상기 가열된 시트에 깊이가 80 ㎛이고, 지름이 70 ㎛인 원추형의 한 쌍의 양각 롤에서 압착 압력을 20 kg/cm로 양각 전사 단계를 거쳐 인수 롤로 이동시켜 제조됨을 특징으로 하는 적층유리용 중간막의 제조방법을 제공한다.The present invention also melts a polyvinyl butyral resin kneaded by adding 40 parts by weight of triethylene glycol-2-ethyl butylate as a plasticizer to 100 parts by weight of polyvinyl butyral with 65 mol% butyralization and 1,700 degree of polymerization as the raw material. After the sheet was prepared by extruding it to a thickness of 1.0 mm by adding it to a bath, and cooling to obtain an elongation rate of 1.3 at the time of moving the sheet with a temperature control roll to complete the sheet, the sheet was formed on the surface of the sheet using a heating plate. The heating step was carried out so that the temperature was 100 ° C. and 60 ° C. at the center, and the pressing pressure was embossed at 20 kg / cm in a pair of conical embossed rolls having a depth of 80 μm and a diameter of 70 μm on the heated sheet. Provided is a method for producing an interlayer film for laminated glass, characterized in that the step is moved to the take-up roll through the step.

이하 본 발명에 첨부된 도면을 참조하여 본 발명의 바람직한 일실시예를 상세히 설명하기로 한다. 우선, 도면들 중, 동일한 구성요소 또는 부품들은 가능한 동일한 참조부호를 나타내고 있음에 유의하여야 한다. 본 발명을 설명함에 있어, 관련된 공지기능 혹은 구성에 대한 구체적인 설명은 본 발명의 요지를 모호하지 않게 하기 위하여 생략한다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. First of all, it should be noted that in the drawings, the same components or parts denote the same reference numerals as much as possible. In describing the present invention, detailed descriptions of related well-known functions or configurations are omitted in order not to obscure the subject matter of the present invention.

본 명세서에서 사용되는 정도의 용어 "약", "실질적으로" 등은 언급된 의미에 고유한 제조 및 물질 허용오차가 제시될 때 그 수치에서 또는 그 수치에 근접한 의미로 사용되고, 본 발명의 이해를 돕기 위해 정확하거나 절대적인 수치가 언급된 개시 내용을 비양심적인 침해자가 부당하게 이용하는 것을 방지하기 위해 사용된다.As used herein, the terms "about", "substantially", and the like, are used at, or in close proximity to, numerical values when manufacturing and material tolerances inherent in the meanings indicated are intended to aid the understanding of the invention. Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers.

도 2는 본 발명의 바람직한 일실시예에 따른 적층유리용 중간막의 제조 장치 단면도이다.Figure 2 is a cross-sectional view of the manufacturing apparatus of the interlayer film for laminated glass according to an embodiment of the present invention.

또한, 도 3은 본 발명의 바람직한 일실시예에 따른 적층유리용 중간막의 제조 공정도이다. 도 3을 참조하면, 본 발명의 적층유리용 중간막은 시트 제조 단계 S100, 가열 단계 S200 및 양각 전사 단계 S300으로 진행될 수 있다.In addition, Figure 3 is a manufacturing process diagram of the interlayer film for laminated glass according to an embodiment of the present invention. Referring to FIG. 3, the interlayer film for laminated glass of the present invention may proceed to a sheet manufacturing step S100, a heating step S200, and an embossed transfer step S300.

도 2 및 도 3을 참조하여 설명하면, 우선, 시트 제조 단계 S100 에 있어서, 시트는 압출성형법으로 제조하되, 원료를 용융조 100 에 투입하여 배출된 시트는 바로 가이드 롤(Guide roll) 111 및 113 에 의해 냉각조 130 으로 이동되고, 이때 냉각조 130 안에서 냉각시킨다. 상기 냉각 방식은 수욕, 롤, 벨트, 에어 등이 이용될 수 있으며, 이에 제한되지 않는다. 상기 냉각된 시트 400 은 연속적으로 한 쌍의 물기 빼기 롤 151 및 153 에 의해 냉각조에서 빠져나와 세 개의 온도조정 롤 171, 173 및 175 로 이동되어, 이를 거쳐 소정의 온도가 조정됨으로써 시트가 제조된다. Referring to Figures 2 and 3, first, in the sheet manufacturing step S100, the sheet is produced by the extrusion molding method, the sheet discharged by putting the raw material into the molten bath 100 is directly guide rolls (Guide roll) 111 and 113 It is moved to the cooling tank 130 by this, and it cools in the cooling tank 130 at this time. The cooling method may be a water bath, a roll, a belt, air, or the like, but is not limited thereto. The cooled sheet 400 is successively pulled out of the cooling tank by a pair of drain rolls 151 and 153 and moved to three temperature adjusting rolls 171, 173 and 175 whereby a predetermined temperature is adjusted to produce a sheet. .

상기 제조된 시트의 두께는 0.1 내지 3.0 mm 이고, 신장율이 1.0 내지 3.0 임이 바람직하다. 왜냐하면, 상기 시트의 두께가 0.1 mm 미만인 경우, 중간막이 너무 얇야져 양각의 전사가 어려우며, 3.0 mm 를 초과하면 이후 중간막의 상하로 유리가 적층된 후의 유리의 투명성이 저하될 우려가 있기 때문이다. 또한, 신장율이 1.0 미만인 경우, 시트의 수축률이 높아 안정한 중간막의 제조가 어렵고, 3.0 을 초과하면 중간막이 흘러내릴 우려가 있다.The thickness of the prepared sheet is 0.1 to 3.0 mm, elongation is preferably 1.0 to 3.0. This is because, when the thickness of the sheet is less than 0.1 mm, the interlayer film should be too thin, which makes it difficult to transfer the embossed material. If the sheet exceeds 3.0 mm, the transparency of the glass after lamination of the glass above and below the interlayer film may be deteriorated. In addition, when the elongation is less than 1.0, the sheet has a high shrinkage ratio, making it difficult to manufacture a stable interlayer, and when the elongation exceeds 3.0, the interlayer may flow.

한편, 상기 시트의 원료는 열가소성 수지로서, 염화비닐계, 아크릴(Acryl) 계, 폴리에스테르(Polyester)계, 올레핀(Olefin)계, 부티랄(Butyral)계, 폴리카보네이트(Polycarbonate)계, 폴리이미드(Polyimide)계, 폴리아미드(Polyamide)계 수지 등이 사용될 수 있으며, 이에 제한되지 않는다.On the other hand, the raw material of the sheet is a thermoplastic resin, vinyl chloride, acrylic, polyester, olefin (Olefin), butyral, polycarbonate, polyimide (Polyimide), polyamide (Polyamide) resin may be used, but is not limited thereto.

상기 원료에는 가소제가 첨가될 수 있는데, 특히 부티랄계 수지에는 가소제가 첨가됨이 바람직하다. 상기 가소제로 트리에틸렌 글리콜-2-에틸부틸레이트(Triethylene glycol-2-ethyl butylate), 테트라에틸렌 글리콜-2-에틸 부틸레이트(Tetraethylene glycol-2-ethyl butylate), g-부틸 지그 리콜 아디페이트(g-Butyl jig recall adiphate)가 사용될 수 있으며, 이에 제한되지 않는다.A plasticizer may be added to the raw material, and particularly preferably, a plasticizer is added to the butyral resin. As the plasticizer, triethylene glycol-2-ethyl butylate, tetraethylene glycol-2-ethyl butylate, g-butyl zigcol adipate (g Butyl jig recall adiphate) may be used, but is not limited thereto.

이후, 상기 제조된 시트 400 에 가열 단계 S200 이 진행될 수 있는데, 상기 가열 단계는 양각이 정확하게 전사되고, 양각이 용이하도록 후술할 양각 전사 단계 S300 의 바로 직전에 가열 장치 200 으로 상기 제조된 시트 400 의 표면부의 온도를 중심부의 온도보다 높게 조절하여 가열시킨다. 따라서, 상기 시트의 표면부를 가열할 때, 가열 장치 200 으로 조절될 가열 온도는 열가소성 수지 시트의 종류에 따라 다르지만, 가소제가 첨가된 폴리비닐 부티랄 수지가 사용되는 경우, 100 내지 200 ℃로 가열됨이 바람직하고, 120 내지 160 ℃로 가열됨이 더욱 바람직하다. 상기 가열 온도는 시트 표면부의 온도가 중심부의 온도보다 5 내지 60 ℃ 정도 높게 조절함이 바람직하고, 더욱 바람직하게는 20 내지 40 ℃ 정도 높게 조절한다. 상기 온도 범위에서 5 ℃ 미만으로 차이가 나면, 시트의 이동 시 장력에 연장되어 늘어나고, 양각 전사 후 제조된 중간막에 뱅크 발생이나 잔류 왜곡이 생길 우려가 있으며, 온도 차이가 60 ℃를 초과하면, 양각 전사율이 떨어질 우려가 있다. 이에, 상 기 가열 장치 200 로는 표면부의 온도가 내부, 즉 중심부의 온도보다 높게 조절 할 수 있는 장치면 어떤 것이든 가능하며, 발열판이나 대기압 플라즈마가 사용될 수 있으며, 이에 제한되지 않는다. 상기 발열판 또는 대기압 플라즈마가 표면부를 가열 시킬 때, 발열판의 위치나 면적, 시트의 열전달 각도 등을 조절하여 온도를 제어할 수 있다. Thereafter, the heating step S200 may be performed on the manufactured sheet 400, wherein the heating step is performed by the heating apparatus 200 immediately before the relief transfer step S300, which will be described later, so that the relief is easily transferred. The temperature of the surface portion is adjusted to be higher than the temperature of the center portion and heated. Therefore, when heating the surface portion of the sheet, the heating temperature to be controlled by the heating device 200 depends on the type of thermoplastic resin sheet, but when polyvinyl butyral resin to which a plasticizer is added is heated to 100 to 200 ° C It is preferable, and it is more preferable to heat to 120-160 degreeC. The heating temperature is preferably adjusted to a temperature of about 5 to 60 ℃ higher than the temperature of the center portion of the sheet surface portion, more preferably 20 to 40 ℃ higher. If the difference is less than 5 ℃ in the above temperature range, it is extended to the tension during the movement of the sheet and stretched, there is a fear that banking or residual distortion occurs in the interlayer manufactured after embossed transfer, if the temperature difference exceeds 60 ℃, embossed There is a risk that the transfer rate will drop. Thus, the heating device 200 may be any device capable of adjusting the temperature of the surface portion higher than the temperature of the inside, that is, the center portion, and a heating plate or an atmospheric pressure plasma may be used, but is not limited thereto. When the heating plate or the atmospheric plasma heats the surface portion, the temperature may be controlled by adjusting the position or area of the heating plate, the heat transfer angle of the sheet, and the like.

본 발명에서 열가소성 수지의 시트 표면부의 온도가 중심부보다 높기 때문에 양각의 형상이 미세하게 깊고, 정확하게 전사된다. 또한, 시트의 중심부의 온도가 상대적으로 표면부의 온도보다 낮기 때문에 시트의 반송 시 장력에도 시트가 연장되지 않고, 잔류 왜곡이 없으며, 가열 수축률이 낮아 적층유리용 중간막에 사용될 경우, 적층유리 제조 시에 불량률이 감소될 수 있다. 그 밖에 양각 롤이 시트로 침투되기 용이하여 뱅크 발생이 없고, 안정적으로 연속적인 시트의 양각 성형이 가능하다.In the present invention, since the temperature of the sheet surface portion of the thermoplastic resin is higher than the central portion, the shape of the relief is finely deep and accurately transferred. In addition, since the temperature at the center of the sheet is relatively lower than the temperature of the surface portion, the sheet does not extend even when the sheet is conveyed, there is no residual distortion, and the heat shrinkage rate is low, when used in the interlayer film for laminated glass, Defective rate can be reduced. In addition, the embossed roll easily penetrates into the sheet, so that no bank is generated, and the continuous sheet can be embossed stably.

마지막으로, 상기 가열 단계를 거친 시트에 양각 전사 단계 S300 을 진행시켜 본 발명의 적층유리용 중간막의 제조가 완성될 수 있다. 상기 양각 전사 방식은 시트 400 에 양각(Emboss) 형상을 전사시키되, 한 쌍의 양각 롤 300 이나 금속 벨트(Belt)가 사용될 수 있으며, 이에 제한되지 않는다. 상기 양각 롤 300 은 금속 롤에 양각 형상이 부여되어 있는 것으로, 상기 양각 형상의 부여 방식은 금속 롤에 조각, 부식, 샌드 블라스트(Sand Blast) 방식으로 양각이 부여된 후, 롤 표면에 도금, 세라믹(Ceramic), 실리콘 코트(Silicon court), 테프론 코트(Teflon court) 등의 처리가 행해질 수 있다. 또한, 양각 전사 시에 온도 제어가 가능한 것이 바람직 하고, 제어 방식은 제한되지 않는다. 한편, 금속 벨트는 벨트의 양단을 용접하여 접합하여 이루어진 루프 상의 것이 바람직하다.Finally, the embossed transfer step S300 to the sheet subjected to the heating step may be completed to manufacture the interlayer film for laminated glass of the present invention. The embossed transfer method transfers an emboss shape to the sheet 400, but a pair of embossed rolls 300 or a metal belt may be used, but is not limited thereto. The embossed roll 300 is embossed to the metal roll, the embossing method is applied to the metal roll by engraving, corrosion, sand blast (Sand Blast) method, the surface of the roll, plating, ceramic (Ceramic), a silicon court, a Teflon court, or the like can be performed. In addition, it is preferable that temperature control is possible at the time of embossing transfer, and the control system is not limited. On the other hand, the metal belt is preferably on the loop formed by welding both ends of the belt.

상기의 양각 전사는 시트의 상하 양면에 동시에 부여되거나 구별된 공정으로 2단으로 진행 될 수 있다.The embossed transfer can be carried out in two stages at the same time or a distinct process on the upper and lower sides of the sheet.

또한, 상기 양각 전사 단계에 있어서, 양각 롤 300 이 열가소성 수지의 시트 400 에 가해지는 압력은 시트의 종류 또는 양각의 형상에 따라 다르며, 10 내지 100 kg/cm 임이 바람직하다. 왜냐하면, 상기 압력이 10 kg/cm 미만인 경우, 양각의 침투가 불완전할 수 있으며, 100 kg/cm를 초과하는 경우 시트의 안정성이 저하될 수 있기 때문이다. 따라서, 가소제화된 폴리비닐 부티랄 수지로 이루어진 시트의 경우, 시트의 표면부의 온도를 130 ℃, 중심부의 온도를 60 ℃로 조절하고, 양각 롤 300 은 깊이가 80 ㎛ 이고, 지름이 70 ㎛ 인 원추형으로 압착 압력이 20 kg/cm 임이 바람직하다.In addition, in the embossed transfer step, the pressure applied to the sheet 400 of the embossed roll 300 depends on the type of the sheet or the shape of the embossed, preferably 10 to 100 kg / cm. Because, when the pressure is less than 10 kg / cm, the embossed penetration may be incomplete, if the pressure exceeds 100 kg / cm, the stability of the sheet may be lowered. Therefore, in the case of a sheet made of plasticized polyvinyl butyral resin, the temperature of the surface portion of the sheet is adjusted to 130 ° C. and the temperature of the center portion to 60 ° C., and the relief roll 300 has a depth of 80 μm and a diameter of 70 μm. Preferably, the conical shape has a compression pressure of 20 kg / cm.

상술한 바와 같이 본 발명의 적층유리용 중간막은 두 형태의 시트가 아닌 한 형태로 시트를 형성시키고, 열가소성 시트가 양각 롤에 침투하기 직전에 열을 부여하여 연속적으로 공정이 진행되어 점착 및 코팅 단계를 배제시킴으로서 공정의 단순화를 통해 제품의 원가가 절감되는 효과가 있고,이와 더불어 양각이 정확하게 전사되도록 하며, 양각 롤의 침투가 양호하여 양각의 전사가 용이한 효과가 있다. As described above, the interlayer film for laminated glass of the present invention forms a sheet in a form other than two types of sheets, and a process is continuously performed by applying heat immediately before the thermoplastic sheet penetrates the embossed roll, thereby adhering and coating. By excluding the process, the cost of the product can be reduced through the simplification of the process, and the relief of the relief can be accurately transferred, and the penetration of the relief roll has the effect of easy transfer of the relief.

또한, 열가소성 시트가 양각 롤에 침투하기 직전에 열을 부여할 때, 시트의 표면을 가열하여 시트 내부인 중심부와 온도 차이를 두어 표면에 양면 또는 편면에 양각의 적용이 자유롭고, 막 흘러내림이 일어나지 않으며, 뱅크 발생이 없고, 잔류 왜곡 및 가열 수축률이 낮은 효과가 있다. In addition, when heat is applied immediately before the thermoplastic sheet penetrates the embossing roll, the surface of the sheet is heated to have a temperature difference from the center of the sheet so that embossing is freely applied to both surfaces or one side on the surface, and film flow does not occur. There is no bank generation, and there is an effect of low residual distortion and low heat shrinkage.

하기의 실시예를 통하여 좀 더 상세하게 설명하고자 한다. Through the following examples will be described in more detail.

실시예 1Example 1

1. 시트 제조 단계 1. Sheet manufacturing steps

부티랄화 65 mol%, 중합도 1,700의 폴리비닐 부티랄 100 중량부에 가소제로 트리에틸렌 글리콜-2-에틸 부틸레이트 40 중량부를 첨가하여 혼련시킨 폴리비닐 부티랄 수지를 도 2 의 용융조 100 에 투입하여 두께가 1.0 mm 되도록 압출하여 시트를 제조한 후, 냉각하여 온도 조절 롤 171, 173 및 175 로 시트 이동 시 신장율 1.3 이 되도록 하여 시트를 완성시켰다.A polyvinyl butyral resin kneaded by adding 40 parts by weight of triethylene glycol-2-ethyl butyrate as a plasticizer to 100 parts by weight of polyvinyl butyral with 65 mol% butyralization and a polymerization degree of 1,700 was added to the melting tank 100 of FIG. The sheet was prepared by extrusion to a thickness of 1.0 mm, and then cooled to complete elongation of 1.3 when the sheet moved to the temperature control rolls 171, 173, and 175 to complete the sheet.

2. 가열 단계2. heating stage

상기 제조된 시트에 발열판을 이용하여 시트의 표면부에 온도 100 ℃ 및 중심부에 60 ℃ 가 되도록 가열 단계를 진행 시켰다.The heating step was carried out using a heating plate in the prepared sheet so that the temperature on the surface portion of the sheet is 100 ℃ and 60 ℃ in the center.

3. 양각 전사 단계3. Embossed Warrior Stage

상기 가열된 시트에 깊이가 80 ㎛이고, 지름이 70 ㎛인 원추형의 한 쌍의 양각 롤 300 에서 압착 압력을 20 kg/cm로 전사시킨 후, 인수 롤 310 으로 이동시켜 적층유리용 중간막을 완성시켰다.The pressure was transferred to the heated sheet at a pressure of 20 kg / cm in a pair of embossed rolls of conical rolls having a depth of 80 µm and a diameter of 70 µm, and then transferred to the take-up roll 310 to complete the interlayer film for laminated glass. .

실시예 2Example 2

실시예 1과 동일하되, 양각 전사 단계에 있어서, 양각 롤의 압착 압력을 70 kg/cm로 전사시켰다.As in Example 1, but in the embossed transfer step, the pressing pressure of the embossed roll was transferred to 70 kg / cm.

실시예 3Example 3

실시예 1과 동일하되, 시트 제조 단계에서 신장률을 1.7로 조절하였고, 가열 단계에서 표면부의 온도가 130 ℃가 되도록 가열하였으며, 양각 전사 단계에서 압착 압력을 40 kg/cm로 전사시켰다.In the same manner as in Example 1, the elongation was adjusted to 1.7 in the sheet manufacturing step, the heating was performed so that the temperature of the surface portion is 130 ° C, and the compression pressure was transferred to 40 kg / cm in the embossed transfer step.

비교예 1Comparative Example 1

부티랄화 65 mol%, 중합도 1,700의 폴리비닐 부티랄 100 중량부에 가소제로 트리에틸렌 글리콜-2-에틸 부틸레이트 40 중량부를 첨가하여 혼련시킨 폴리비닐 부티랄 수지를 도 1 의 용융조 1, 2 및 3 에 투입하여 용융조 1 및 3 에서 압출된 시트 11 및 13의 두께는 0.1 mm 이고, 용융조 2 에서 압출된 시트 12 의 두께는 0.8 mm가 되도록 제조한 후, 시트 12 는 가이드 롤 4a 및 4b 로 냉각조 5 에 이동시켜 냉각 시킨다. 이후, 시트 11 및 13 은 온도 조절 롤 108a, 108b 및 108c 을 거치며, 시트에 온도 100 ℃ 로 부여하고, 신장율 1.3 이 되도록 시트를 제조하였다. 이와 동시에 시트 12 에는 온도 60 ℃ 로 부여하고, 신장율 1.0 이 되도록 하여 시트를 제조하였다. 상기 제조된 시트 11 및 13 사이에 시트 12 가 적층되도록, 깊이가 80 ㎛이고, 지름이 70 ㎛인 원추형의 한 쌍의 양각 롤 9 에서 각 시트를 함께 적층함과 동시에 압착 압력 20 kg/cm 로 시트 11 및 13 에 양각을 전사시킨 후, 인수 롤 10 으로 이동시켜 적층유리용 중간막을 완성시켰다.The polyvinyl butyral resin kneaded by adding 40 parts by weight of triethylene glycol-2-ethyl butyrate as a plasticizer to 100 parts by weight of polyvinyl butyral with 65 mol% butyralization and a degree of polymerization of 1,700 was dissolved in the melting tanks 1, 2 and The thicknesses of the sheets 11 and 13 which were put into 3 and extruded from the melting tanks 1 and 3 were 0.1 mm, and the melting tank was After the sheet 12 extruded at 2 was manufactured to have a thickness of 0.8 mm, the sheet 12 was moved to the cooling tank 5 with guide rolls 4a and 4b and cooled. Thereafter, the sheets 11 and 13 were subjected to temperature control rolls 108a, 108b, and 108c, and the sheets were given at a temperature of 100 ° C., and a sheet was prepared such that the elongation was 1.3. At the same time, the sheet 12 was prepared at a temperature of 60 ° C. to have an elongation of 1.0. The sheet 12 is laminated between the prepared sheets 11 and 13 at a compression pressure of 20 kg / cm while stacking the sheets together in a pair of embossed rolls 9 having a depth of 80 µm and a diameter of 70 µm. After embossing the sheets 11 and 13, the sheet was moved to the transfer roll 10 to complete the interlayer film for laminated glass.

비교예 2Comparative Example 2

비교예 1과 동일하되, 양각롤 9 에서 압착 압력 70 kg/cm로 양각을 전사시켰다.In the same manner as in Comparative Example 1, the relief was transferred to a pressing pressure of 70 kg / cm in the relief roll 9.

비교예 3Comparative Example 3

비교예 1과 동일하되, 시트 11 및 13 은 온도 조절 롤 108a, 108b 및 108c 을 거치며, 시트에 온도 130 ℃ 로 부여하고, 신장율 1.3 이 되도록 시트를 제조하였으며, 양각 롤 9 에서 각 시트를 함께 적층함과 동시에 압착 압력 40 kg/cm로 시트 11 및 13 에 양각을 전사시켰다. In the same manner as in Comparative Example 1, sheets 11 and 13 were subjected to temperature control rolls 108a, 108b, and 108c, and the sheets were given at a temperature of 130 ° C., and sheets were prepared to have an elongation of 1.3. At the same time, relief was transferred to sheets 11 and 13 at a compression pressure of 40 kg / cm.

* 시험방법* Test Methods

1. 막 흘러내림성1. Membrane running down

양각 롤에 들어가기 전, 시트의 상태를 육안 관찰하고, 롤의 전면부에서 시트가 떨어지거나 끊기는 상태를 X, 상기의 경우가 발생하지 않은 상태를 O 로 표기 한다.Before entering the embossed roll, the state of the sheet is visually observed, and the state where the sheet falls or breaks off the front part of the roll is denoted by X, and the state in which the above case does not occur is denoted by O.

2. 양각 롤의 침투성2. Permeability of Embossed Roll

시트에 양각 롤이 침투할 때의 침투성을 육안 관찰하고, 뱅크 발생 및 안정한 성형이 이루어지지 않은 것을 X, 뱅크의 발생이 없고, 침투가 양호한 것을 O 로 표기 한다.The permeability at the time when the embossed roll penetrates into a sheet | seat is visually observed, and X and the occurrence of a bank which do not generate | occur | produce a bank and stable shaping | molding are not formed, and a penetration is good, and it denotes O.

3. 양각 전사율3. Embossed transfer rate

양각이 전사되어 완성된 시트를 ISO3274에 준하여 10 점 만점으로 하여, 평균 표면 거칠기 Rz를 계측하고 전사율을 산출하였다.The embossed transfer sheet was made a perfect score of 10 points according to ISO3274, and the average surface roughness Rz was measured and the transfer rate was calculated.

4. 가열 수축률4. Heating Shrinkage

양각이 전사되어 완성된 시트를 90 ℃의 온수에 1 분간 침지한 뒤, 시트의 치수변화를 측정하고, 가열 수축률을 구하였다.After the embossed transfer sheet was immersed in hot water at 90 ° C. for 1 minute, the dimensional change of the sheet was measured and the heat shrinkage was calculated.

상기의 방법으로 시험한 측정결과는 하기와 같다.The measurement results tested by the above method are as follows.

구분division 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3 시트 11 및 13 / 시트 12Sheet 11 and 13 / Sheet 12 조건  Condition 두께, mmThickness, mm 1One 1One 1One 0.1/0.80.1 / 0.8 0.1/0.80.1 / 0.8 0.1/0.80.1 / 0.8 신장율Elongation 1.31.3 1.31.3 1.71.7 1.3/1.01.3 / 1.0 1.3/1.01.3 / 1.0 1.7/1.01.7 / 1.0 표면부온도, ℃Surface temperature, 100100 100100 130130 100100 100100 130130 중심부 온도, ℃Core temperature, ℃ 6060 6060 6060 6060 6060 6060 압착 압력, kg/cm Crimping pressure, kg / cm 2020 7070 4040 2020 7070 4040 결과 result 막흘러내림성Shedding OO OO OO OO OO OO 양각 롤의 침투성Permeability of Embossed Roll OO OO OO OO OO OO 양각 전사율, %Embossed Transfer Rate,% 9999 9898 9999 9595 9999 9999 가열 수축률, %Heating shrinkage,% -1.8-1.8 -2.0-2.0 -2.5-2.5 -2.3-2.3 -2.4-2.4 -3.0-3.0

상기 표 1에서 나타난 바와 같이, 본 발명에 의해 제조된 실시예 1, 2 및 3 의 방법으로 제조된 적층유리용 중간막은 비교예 1, 2 및 3 과 비교하여 모두 유사하게 양호한 특성을 나타내었으며, 특히 가열 수축률은 더욱 탁월함을 확인하였다.As shown in Table 1, the interlayer film for laminated glass manufactured by the method of Examples 1, 2 and 3 according to the present invention showed similarly good characteristics in comparison with Comparative Examples 1, 2 and 3, In particular, the heat shrinkage rate was confirmed to be more excellent.

이상에서 설명한 본 발명은 전술한 실시예 및 첨부된 도면에 의해 한정되는 것이 아니고, 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 여러 가지 치환, 변형 및 변경이 가능함은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에게 있어서 명백할 것이다.The present invention described above is not limited to the above-described embodiment and the accompanying drawings, and various substitutions, modifications, and changes are possible within the scope without departing from the technical spirit of the present invention. It will be evident to those who have knowledge of.

도 1은 기존의 적층유리용 중간막의 제조 장치 단면도.1 is a cross-sectional view of a manufacturing apparatus of a conventional interlayer film for laminated glass.

도 2는 본 발명의 바람직한 일실시예에 따른 적층유리용 중간막의 제조 장치 단면도.Figure 2 is a cross-sectional view of the manufacturing apparatus of the interlayer film for laminated glass according to an embodiment of the present invention.

도 3은 본 발명의 바람직한 일실시예에 따른 적층유리용 중간막의 제조 공정도.Figure 3 is a manufacturing process of the interlayer film for laminated glass according to an embodiment of the present invention.

<도면의 주요 부호에 대한 설명><Description of Major Symbols in Drawing>

1, 2, 3, 100 : 용융조, 4a, 4b, 111, 113 : 가이드 롤 1, 2, 3, 100: molten bath, 4a, 4b, 111, 113: guide roll

5,130 : 냉각조5,130: cooling tank

6a,6b,6c,7a,7b,: 온도 조정 롤, 8, 151, 153 : 물기 빼기 롤6a, 6b, 6c, 7a, 7b,: Temperature adjusting roll, 8, 151, 153: Drain roll

200 : 시트 가열 장치 200: sheet heating device

9, 300 : 양각 롤, 10, 310 : 인수 롤9, 300: embossed roll, 10, 310: takeover roll

11, 12, 13, 400 : 열가소성 수지 시트11, 12, 13, 400: thermoplastic resin sheet

Claims (18)

적층유리용 중간막에 있어서,In the interlayer film for laminated glass, 원료가 압출되어 이루어진 시트를 양각 전사 직전에 표면부와 중심부에 온도차를 두고 가열시켜, 시트의 표면부가 양각되어 이루어짐을 특징으로 한 적층유리용 중간막.An interlayer film for laminated glass, wherein a sheet formed by extruding raw materials is heated with a temperature difference between the surface portion and the center portion just before embossing transfer, and the surface portion of the sheet is embossed. 제1항에 있어서,The method of claim 1, 상기 원료는 염화비닐계, 아크릴계, 폴리에스테르계, 올레핀계, 부티랄계, 폴리카보네이트계, 폴리이미드계 및 폴리아미드계 수지가 포함되어 이루어진 군에서 1 이상 선택되어 포함됨을 특징으로 하는 적층유리용 중간막.The raw material is at least one selected from the group consisting of vinyl chloride, acrylic, polyester, olefin, butyral, polycarbonate, polyimide and polyamide resin is selected from the interlayer film for laminated glass . 제2항에 있어서,The method of claim 2, 상기 원료가 부티랄계 수지로 이루어진 경우, 가소제가 첨가되되, 트리에틸렌 글리콜-2-에틸부틸레이트, 테트라에틸렌 글리콜-2-에틸 부틸레이트 및 g-부틸 지그 리콜 아디페이트가 포함되어 이루어진 군에서 1 이상 선택되어 가소화됨을 특징으로 하는 적층유리용 중간막.When the raw material is made of a butyral resin, a plasticizer is added, and at least one from the group consisting of triethylene glycol-2-ethyl butyrate, tetraethylene glycol-2-ethyl butyrate and g-butyl zigcol adipate An interlayer film for laminated glass, which is selected and plasticized. 제1항에 있어서,The method of claim 1, 상기 시트의 두께가 0.1 내지 3.0 mm 이고, 신장율이 1.0 내지 3.0 임을 특 징으로 하는 적층유리용 중간막.The interlayer film for laminated glass, characterized in that the thickness of the sheet is 0.1 to 3.0 mm, elongation is 1.0 to 3.0. 제1항에 있어서,The method of claim 1, 상기 표면부의 온도가 중심부의 온도 보다 5 내지 60 ℃ 높게 가열됨을 특징으로 하는 적층유리용 중간막.The interlayer film for laminated glass, characterized in that the temperature of the surface portion is heated to 5 to 60 ℃ higher than the temperature of the central portion. 적층유리용 중간막의 제조방법에 있어서,In the manufacturing method of the interlayer film for laminated glass, 원료가 압출되어 이루어지는 시트 제조 단계;A sheet manufacturing step in which the raw material is extruded; 상기 제조된 시트가 표면부와 중심부에 온도차를 두어 양각 전사 직전에 가열되는 가열 단계; 및 A heating step in which the manufactured sheet is heated just before embossing transfer with a temperature difference between a surface portion and a center portion; And 상기 가열된 시트의 표면부에 요철이 형성되는 양각 전사 단계가 연속적으로 이루어짐을 특징으로 하는 적층유리용 중간막의 제조방법.Method of producing an interlayer film for laminated glass, characterized in that the embossing transfer step of forming the irregularities in the surface portion of the heated sheet is made continuously. 제6항에 있어서,The method of claim 6, 상기 시트 제조 단계에 있어서, 상기 원료는 염화비닐계, 아크릴계, 폴리에스테르계, 올레핀계, 부티랄계, 폴리카보네이트계, 폴리이미드계 및 폴리아미드계 수지가 포함되어 이루어진 군에서 1 이상 선택되어 이루어짐을 특징으로 하는 적층유리용 중간막의 제조방법.In the sheet manufacturing step, the raw material is at least one selected from the group consisting of vinyl chloride, acrylic, polyester, olefin, butyral, polycarbonate, polyimide and polyamide resin. The manufacturing method of the interlayer film for laminated glass characterized by the above-mentioned. 제7항에 있어서,The method of claim 7, wherein 상기 원료가 부티랄계 수지로 이루어진 경우, 가소제가 첨가되되, 트리에틸렌 글리콜-2-에틸부틸레이트, 테트라에틸렌 글리콜-2-에틸 부틸레이트 및 g-부틸 지그 리콜 아디페이트가 포함되어 이루어진 군에서 1 이상 선택되어 가소화됨을 특징으로 하는 적층유리용 중간막의 제조방법.When the raw material is made of a butyral resin, a plasticizer is added, and at least one from the group consisting of triethylene glycol-2-ethyl butyrate, tetraethylene glycol-2-ethyl butyrate and g-butyl zigcol adipate Method for producing an interlayer film for laminated glass, characterized in that the plasticized by selecting. 제6항에 있어서,The method of claim 6, 상기 시트의 두께가 0.1 내지 3.0 mm 이고, 신장율이 1.0 내지 3.0 임을 특징으로 하는 적층유리용 중간막의 제조방법.The thickness of the sheet is 0.1 to 3.0 mm, the elongation is 1.0 to 3.0 characterized in that the manufacturing method of the interlayer film for laminated glass. 제6항에 있어서,The method of claim 6, 상기 가열 단계에 있어서, 표면부의 온도가 중심부의 온도 보다 5 내지 60 ℃ 높게 가열됨을 특징으로 하는 적층유리용 중간막의 제조방법.In the heating step, the temperature of the surface portion is a method for producing an interlayer film for laminated glass, characterized in that the heating is 5 to 60 ℃ higher than the temperature of the center portion. 제6항에 있어서,The method of claim 6, 상기 가열 단계에 있어서, 가열 장치는 발열판이나 대기압 플라즈마가 이용되어 가열됨을 특징으로 하는 적층유리용 중간막의 제조방법. In the heating step, the heating device is a method of manufacturing an interlayer film for laminated glass, characterized in that the heating using a heating plate or atmospheric pressure plasma. 제6항에 있어서,The method of claim 6, 상기 양각 전사 단계에 있어서, 양각 전사는 시트의 상하 양면에 동시에 부여되거나 구별된 공정으로 2단으로 진행됨을 특징으로 하는 적층유리용 중간막의 제조방법.In the embossed transfer step, the embossed transfer is a method for producing an interlayer film for laminated glass, characterized in that proceeded in two stages at the same time given to the upper and lower sides of the sheet or in a distinct process. 제6항에 있어서,The method of claim 6, 상기 양각 전사 단계에 있어서, 시트에 양각 전사 방식은 한 쌍의 양각 롤이나 금속 벨트가 이용되어 양각이 전사됨을 특징으로 하는 적층유리용 중간막의 제조방법.In the embossed transfer step, the embossed transfer method to the sheet is a method of manufacturing an interlayer film for laminated glass, characterized in that the embossed transfer using a pair of embossed rolls or metal belts. 제13항에 있어서,The method of claim 13, 상기 금속 벨트는 벨트의 양단을 용접하여 접합하여 이루어진 루프 상의 것임을 특징으로 하는 적층유리용 중간막의 제조방법.The metal belt is a method of manufacturing an interlayer film for laminated glass, characterized in that the loop is formed by welding both ends of the belt. 제13항에 있어서,The method of claim 13, 상기 양각 롤 또는 금속 벨트에 양각 부여 방식은 조각, 부식 또는 샌드 블라스트 방식으로 양각이 부여된 후, 표면에 도금, 세라믹, 실리콘 코트 또는 테프론 코트 처리가 행해져 이루어짐을 특징으로 하는 적층유리용 중간막의 제조방법.The embossing method to the embossing roll or metal belt is the engraving, corrosion or sand blast method of embossing, after the surface is plated, ceramic, silicon coat or Teflon coating is made of the manufacturing of the interlayer film for laminated glass Way. 제6항에 있어서,The method of claim 6, 상기 양각 전사 단계에 있어서, 양각 전사 시에 온도 제어가 가능한 것을 특징으로 하는 적층유리용 중간막의 제조방법.In the embossed transfer step, the temperature control at the time of embossed transfer, the manufacturing method of the interlayer film for laminated glass. 제6항에 있어서,The method of claim 6, 상기 양각 전사 단계에 있어서, 양각 롤의 압착 압력이 10 내지 100 kg/cm 인 것을 특징으로 하는 적층유리용 중간막의 제조방법.In the embossed transfer step, the pressing pressure of the embossed roll is 10 to 100 kg / cm manufacturing method of the interlayer film for laminated glass. 제6항에 있어서, The method of claim 6, 상기 원료로서 부티랄화 65 mol%, 중합도 1,700의 폴리비닐 부티랄 100 중량부에 가소제로 트리에틸렌 글리콜-2-에틸 부틸레이트 40 중량부를 첨가하여 혼련시킨 폴리비닐 부티랄 수지를 용융조에 투입하여 두께가 1.0 mm 되도록 압출하여 시트를 제조한 후, 냉각하여 온도 조절 롤로 시트 이동 시 신장율 1.3 이 되도록 하여 시트를 완성시킨 후, 상기 제조된 시트에 발열판을 이용하여 시트의 표면부에 온도 100 ℃ 및 중심부에 60 ℃ 가 되도록 가열 단계를 진행시키고, 상기 가열된 시트에 깊이가 80 ㎛이고, 지름이 70 ㎛인 원추형의 한 쌍의 양각 롤에서 압착 압력을 20 kg/cm로 양각 전사 단계를 거쳐 인수 롤로 이동시켜 제조됨을 특징으로 하는 적층유리용 중간막의 제조방법.As the raw material, polyvinyl butyral resin kneaded by adding 40 parts by weight of triethylene glycol-2-ethyl butylate as a plasticizer to 100 parts by weight of polyvinyl butyral with a butyralization and a polymerization degree of 1,700 was added to the melting tank to obtain a thickness. After the sheet was manufactured by extruding to 1.0 mm, the sheet was cooled and cooled to have an elongation rate of 1.3 at the time of moving the sheet with a temperature control roll, and then the sheet was completed. The heating step proceeds to 60 ° C., and the pressing pressure is transferred to the take-up roll through the embossing transfer step at a pressure of 20 kg / cm in a pair of conical embossed rolls having a depth of 80 μm and a diameter of 70 μm on the heated sheet. Method for producing an interlayer film for laminated glass, characterized in that the manufacture.
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KR20210071208A (en) * 2019-12-06 2021-06-16 에스케이씨 주식회사 Film for bonding and light transmitting layered product comprising of the same
WO2021112625A3 (en) * 2019-12-06 2021-07-29 에스케이씨 주식회사 Bonding film and light-transmitting laminate comprising same

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JPS55133762A (en) 1979-04-06 1980-10-17 Asahi Chem Ind Co Ltd Manufacture of separator with horizontal rib
JP2584883B2 (en) * 1990-03-31 1997-02-26 積水化学工業株式会社 Method for producing embossed polyvinyl acetal resin sheet
JP2001205702A (en) 2000-01-26 2001-07-31 Dainippon Printing Co Ltd Method for manufacturing decorative sheet
KR100361436B1 (en) * 2000-05-27 2002-11-22 김영한 Preparing method of thin film processed with mechanical pattern and apparatus thereof

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KR20210071208A (en) * 2019-12-06 2021-06-16 에스케이씨 주식회사 Film for bonding and light transmitting layered product comprising of the same
WO2021112625A3 (en) * 2019-12-06 2021-07-29 에스케이씨 주식회사 Bonding film and light-transmitting laminate comprising same

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