WO2019073664A1 - Surface-treated, woven or knit glass fiber fabric, and glass-fiber-reinforced silicone resin film material including same - Google Patents

Surface-treated, woven or knit glass fiber fabric, and glass-fiber-reinforced silicone resin film material including same Download PDF

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Publication number
WO2019073664A1
WO2019073664A1 PCT/JP2018/028546 JP2018028546W WO2019073664A1 WO 2019073664 A1 WO2019073664 A1 WO 2019073664A1 JP 2018028546 W JP2018028546 W JP 2018028546W WO 2019073664 A1 WO2019073664 A1 WO 2019073664A1
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Prior art keywords
glass fiber
group
functional group
silane coupling
coupling agent
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PCT/JP2018/028546
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French (fr)
Japanese (ja)
Inventor
聡 三島
和明 南
彰 吉村
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日東紡績株式会社
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Publication of WO2019073664A1 publication Critical patent/WO2019073664A1/en

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    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
    • B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic substance
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain

Definitions

  • the present invention relates to a surface-treated glass fiber woven or knitted fabric and a glass fiber-reinforced silicone resin film material using the same.
  • glass fiber woven fabric and the glass fiber knitted fabric are collectively referred to as "glass fiber woven and knitted fabric”.
  • a coating layer consisting of a silane coupling agent is formed on the surface of the glass fiber to form a surface treated glass fiber woven or knitted fabric. It is Moreover, when forming the coating layer which consists of a silane coupling agent on the surface of glass fiber, it is known to make a coating layer into two layers (for example, refer patent document 1).
  • Patent No. 5845501 gazette
  • An object of the present invention is to provide a surface-treated glass fiber woven or knitted fabric which can eliminate such disadvantages and obtain strong adhesive strength to a silicone resin layer.
  • Another object of the present invention is to provide a glass fiber reinforced silicone resin film material having excellent mechanical strength.
  • the surface-treated glass fiber woven or knitted fabric of the present invention comprises a first surface treated layer comprising a first silane coupling agent and a coating agent on the glass fiber woven / knitted surface, and a second silane.
  • a surface-treated glass fiber woven or knitted fabric comprising a second surface-treated layer containing a coupling agent in this order, wherein the first silane coupling agent is a functional group consisting of a primary amino group and a secondary amino group A second functional group having a first functional group which is one functional group selected from any group of group group A or functional group group B consisting of a terminal vinyl group, a terminal epoxy group and a terminal halogeno group;
  • the silane coupling agent has a second functional group which is one functional group selected from functional group groups different from the functional group group to which the first functional group belongs, and the second silane coupling
  • the mass of the agent is said second surface Characterized in that at least 80 wt% of the total mass physical layer.
  • the surface-treated glass fiber woven or knitted fabric of the present invention comprises a first surface-treated layer containing a first silane coupling agent and a coating agent, and a second surface-treated layer containing a second silane coupling agent on the glass fiber woven / knitted surface.
  • a surface treatment layer is provided in this order.
  • the first silane coupling agent is a functional group group A consisting of a primary amino group and a secondary amino group, or a functional group group B consisting of a terminal vinyl group, a terminal epoxy group and a terminal halogeno group. It has a first functional group which is one functional group selected from any group.
  • the second silane coupling agent has a second functional group which is one functional group selected from functional group groups different from the functional group group from which the first functional group is selected.
  • the second silane coupling agent is selected from the functional group group B. It has 2 functional groups.
  • the first silane coupling agent has a first functional group selected from the functional group group B
  • the second silane coupling agent is selected from the functional group group A. It has 2 functional groups.
  • the mass of the second silane coupling agent is 80% by mass or more of the mass of the entire second surface-treated layer, in addition to the above configuration.
  • a silicone resin layer is provided on the surface treatment layer of 2
  • the adhesive strength strong against the silicone resin layer can be obtained, and the mechanical strength is excellent in the obtained glass fiber reinforced silicone resin film material.
  • the surface-treated glass fiber woven or knitted fabric according to the present invention is provided on the second surface-treated layer except when the first surface-treated layer and the second surface-treated layer have the above-described configuration. Sufficient adhesive strength can not be obtained for the silicone resin layer.
  • the mass of the second silane coupling agent is less than 80% by mass of the mass of the entire second surface-treated layer, the first surface treatment Regardless of the configuration of the layer and the second surface treatment layer, sufficient adhesive strength can not be obtained for the silicone resin layer provided on the second surface treatment layer.
  • the functional group group A comprises a terminal primary amino group
  • the functional group group B comprises a terminal methacryloyl group, a terminal glycidoxy group and a chloro group.
  • the molar ratio of the first silane coupling agent to the second silane coupling agent is in the range of 70:30 to 13:87. preferable.
  • the surface-treated glass fiber woven or knitted fabric of the present invention can obtain stronger adhesive strength to the silicone resin layer provided on the second surface-treated layer.
  • the tensile strength in the warp direction and the weft direction is 1500 N / 25 mm or more.
  • the surface-treated glass fiber woven or knitted fabric of the present invention it is possible to obtain a glass fiber reinforced silicone resin membrane material having excellent strength.
  • the first functional group and the second functional group form a chemical bond.
  • the alkoxy group contained in the second silane coupling agent is hydrolyzed to form a silanol group, and the silanol group is Since it exists on the surface not in contact with the first surface treatment layer of the second surface treatment layer, it is preferable from the viewpoint of improving the adhesive strength to the silicone resin layer provided on the second surface treatment layer. .
  • the glass fiber reinforced silicone resin membrane material of the present invention is an excellent machine by providing the silicone resin layer on the second surface treated layer of the surface treated glass fiber woven or knitted fabric of the present invention having any of the above-mentioned constitutions. Strength can be obtained.
  • the surface-treated glass fiber woven or knitted fabric 1 of the present embodiment comprises a first surface treated layer 3 containing a first silane coupling agent and a coating agent on the surface of the glass fiber woven or knitted fabric 2; And a second surface treatment layer 4 containing two silane coupling agents in this order.
  • the surface-treated glass fiber woven or knitted fabric 1 forms the glass fiber-reinforced silicone resin film material 6 by providing the silicone resin layer 5 on the second surface-treated layer 4.
  • the glass fiber woven or knitted fabric 1 may be a glass fiber woven fabric or a glass fiber woven fabric.
  • the glass fiber woven fabric for example, an untwisted yarn having a weight of 1.5 to 150 tex, a twisted yarn obtained by twisting an untwisted yarn, or a plurality of 50 to 2500 glass filaments having a filament diameter of 3 to 10 ⁇ m are collected.
  • a glass fiber woven fabric having a weight of 10 to 2000 g / m 2 per unit area can be mentioned.
  • the glass fiber knitted fabric for example, an untwisted yarn having a weight of 1.5 to 150 tex, a twisted yarn obtained by twisting an untwisted yarn, or 50 to 2,500 glass filaments having a filament diameter of 3 to 10 ⁇ m are collected.
  • a knitting yarn a glass fiber knitted fabric obtained by tricot knitting, Russell knitting, etc. can be mentioned as a knitting yarn, which is formed by twisting together a plurality of non-twist yarns or twist yarns. Since high tensile strength is obtained, it is preferable to use a glass fiber woven fabric for the surface-treated glass fiber woven or knitted fabric 1 of the present embodiment.
  • flexibility such as an addition reaction curing type silicone elastomer, a condensation reaction curing type silicone elastomer, can be mentioned, for example.
  • the first silane coupling agent contained in the first surface treatment layer 3 is a functional group group A consisting of a primary amino group and a secondary amino group, or a terminal vinyl group, a terminal epoxy group and a terminal halogeno. It has a first functional group which is one functional group selected from any group of functional group group B consisting of groups.
  • the second silane coupling agent contained in the second surface treatment layer 4 is one functional group selected from functional group groups different from the functional group group from which the first functional group is selected. It has a second functional group which is a group.
  • the second silane coupling agent when the first silane coupling agent has a first functional group selected from the functional group group A, the second silane coupling agent is selected from the functional group group B. Having a second functional group.
  • the first silane coupling agent has a first functional group selected from the functional group group B
  • the second silane coupling agent is selected from the functional group group A. It has 2 functional groups.
  • silane coupling agent having a primary amino group examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, and ureidopropyltriol.
  • examples include methoxysilane, ureidopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane.
  • 3-aminopropyltriethoxysilane (molecular weight 221.4) or N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (molecular weight 222.4) having a terminal primary amino group is preferably used. it can.
  • silane coupling agent having a secondary amino group examples include N- (vinylbenzyl-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3- (2-aminoethyl) aminopropyltrimethoxy.
  • Silane 3-phenylaminopropyltrimethoxysilane, ureidopropyltrimethoxysilane, ureidopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3 N- (aminoethyl) -3-aminopropyltrimethoxysilane (molecular weight 222.4) or N- (vinylbenzyl-2-aminoethyl-3-).
  • Aminopropyltrimethoxysilane hydrochloride (molecular weight 375) It can be suitably used.
  • silane coupling agent having a terminal vinyl group examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinylacetoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxy Silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride And the like, but vinyl methoxysilane (molecular weight 148.2), N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl trimethoxysilane hydrochloride (molecular weight 375), 3-acrylic Trimethoxysilane (molecular weight 234.3
  • silane coupling agent having a terminal epoxy group examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxy Propylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. may be mentioned, but 3-glycidoxypropyltrimethoxysilane (molecular weight 234.3) having a terminal glycidoxy group is preferred. It can be used for
  • silane coupling agent having a terminal halogeno group examples include (3-chloropropyl) trimethoxysilane, (3-chloropropyl) triethoxysilane, etc. Chloropropyl) trimethoxysilane can be preferably used.
  • the first surface treatment layer 3 does not contain starch as the coating agent because the adhesion strength of the second surface treatment layer 4 to the silicone resin layer 5 is improved.
  • the mass of the first silane coupling agent can be, for example, in the range of 0.5 to 10 mass% of the mass of the entire first surface treatment layer 3, and preferably The content can be in the range of 0.8 to 8.0% by mass, more preferably 1.0 to 5.0% by mass.
  • the mass of the second silane coupling agent is required to be 80 mass% or more of the mass of the entire second surface treatment layer 4, preferably 90 mass% or more, more preferably 95 mass % Or more, more preferably 99% by mass or more, and particularly preferably, the second surface treatment layer 4 is substantially composed of only the second silane coupling agent.
  • the second surface treatment layer 4 preferably does not contain inorganic particles, for example, a pigment, because the second surface treatment layer 4 may reduce the adhesive strength to the silicone resin layer 5.
  • the total mass of the first silane coupling agent and the second silane coupling agent is, for example, 1.0 of the total mass of the entire first surface treatment layer 3 and the entire second surface treatment layer 4. It can be in the range of 3 to 35.0% by mass, preferably 2.0 to 30.0% by mass, more preferably 5.0 to 20.0% by mass, and still more preferably 5.5 to 18.0%. It can be in the range of%.
  • the total mass of the first silane coupling agent and the second silane coupling agent is, for example, in the range of 0.01 to 0.50 mass% of the mass of the entire surface-treated glass fiber woven or knitted fabric 1. And preferably in the range of 0.015 to 0.15% by mass, more preferably 0.02 to 0.12% by mass.
  • the molar ratio of the first silane coupling agent to the second silane coupling agent can be, for example, in the range of 96: 4 to 4:96, and the surface-treated glass fiber woven or knitted fabric 1 is the silicone.
  • the range of 70:30 to 18:37 is preferable, and the range of 60:40 to 15:85 is more preferable.
  • the weight ratio of the first silane coupling agent to the second silane coupling agent can be, for example, in the range of 96: 4 to 4:96, and in the range of 70:30 to 13:87. Is preferably, and more preferably in the range of 60:40 to 12:88.
  • the first functional group and the second functional group form a chemical bond.
  • the alkoxy group contained in the second silane coupling agent is hydrolyzed to form a silanol group, and the silanol group is It exists on the surface (surface which contacts silicone resin layer 5) which does not contact with the 1st surface treatment layer 3 of the 2nd surface treatment layer 4.
  • the silicone resin layer 5 is formed on the second surface treatment layer 4, the silanol group derived from the second silane coupling agent is —Si—O between the silanol group and the silicone resin layer 5. It is preferable because a -Si- bond can be formed, and the adhesive strength of the second surface treatment layer 4 to the silicone resin layer 5 can be improved.
  • the surface-treated glass fiber woven / knit 1 of the present embodiment in which the first surface-treated layer 3 and the second surface-treated layer 4 are provided in this order on the surface of the glass fiber woven / knit 2 is
  • the tensile strength in the latitudinal direction is preferably 1500 N / 25 mm or more.
  • the tensile strength in the warp direction and in the weft direction of the surface-treated glass fiber woven or knitted fabric 1 is measured in accordance with JIS R 3420.
  • the glass fiber reinforced silicone resin film material 6 is obtained by knife-coating a paste containing a silicone resin monomer on the surface-treated glass fiber woven / knitted material 1 of the present embodiment and providing the silicone resin layer 5 by heat treatment. Can.
  • Examples 1 to 12 First, as shown in Tables 1 and 2, glass fiber woven fabric (warp weave density: 29 yarns / 25 mm, weft weave density: 32 yarns / 25 mm) using glass fiber synthetic twisted yarn (135Tex) as warp yarns and weft yarns
  • the first surface-treated layer of the laminate is formed by using the laminate in which the first surface-treated layer 3 containing the first silane coupling agent S1 is formed on the surface of the woven or knitted fabric 2 and the glass fiber woven / knitted material 2 A second surface treated layer 4 containing a second silane coupling agent S2 was formed on the third surface, and a surface treated glass fiber woven / knitted fabric 1 was produced.
  • the first surface treatment layer 3 further contains a urethane resin as a coating agent.
  • the second surface treatment layer 4 does not contain a pigment.
  • a silicone resin (KE5620W-U made by Shin-Etsu Silicone Co., Ltd.) is applied onto the second surface-treated layer 4 of the surface-treated glass fiber woven / knitted material 1 to a dry weight of 50 g / m 2.
  • the glass fiber reinforced silicone resin film material 6 was produced by drying and forming the silicone resin layer 5.
  • the adhesive strength of the surface-treated glass fiber woven or knitted fabric 1 to the silicone resin layer 5 was measured in accordance with the Japan Membrane Structure Association Test Method Standard “Quality and Performance Test Method of Membrane Material”.
  • the adhesive strength is good when the silicone resin layer 5 can not be peeled off from the surface-treated glass fiber woven / knitted material 1 and damaged ( ⁇ ), but a part of the silicone resin layer 5 remains on the surface-treated glass fiber woven / woven material 1
  • the case where the resin was not completely damaged and peeled off was evaluated as good ( ⁇ ), and the case where the silicone resin layer 5 did not remain on the surface-treated glass fiber woven and knitted fabric 1 and completely peeled off was evaluated as unacceptable ( ⁇ ).
  • silane coupling agent of Table 1 and Table 2 is as follows.
  • Aminosilane 3-aminopropyltriethoxysilane methacrylsilane: 3-methacryloxypropyltrimethoxysilane epoxysilane: 3-glycidoxypropyltrimethoxysilane chlorosilane: (3-chloropropyl) trimethoxysilane diaminosilane: N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane acrylsilane: 3-acryloxypropyltrimethoxysilane vinylsilane: vinyltrimethoxysilane Cationic silane: N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl tri Methoxysilane Hydrochloride Further, “mass%” in Tables 1 to 4 is a value when the mass of only the glass fiber not provided with the surface treatment layer is 100 mass%.
  • a surface-treated glass fiber woven or knitted fabric 1 is produced in the same manner as in Examples 1 to 12 except that the first silane coupling agent S1 and the second silane coupling agent S2 shown in Table 3 are used. did.
  • the first surface treatment layer 3 further contains a urethane resin as a coating agent.
  • a glass fiber reinforced silicone resin film material 6 was produced in the same manner as in Examples 1 to 12 except that the surface-treated glass fiber woven / knitted fabric 1 obtained in Comparative Examples 1 to 7 was used.
  • silane coupling agent of Table 3 is as follows.
  • Aminosilane 3-aminopropyltriethoxysilane methacrylsilane: 3-methacryloxypropyltrimethoxysilane epoxysilane: 3-glycidoxypropyltrimethoxysilane chlorosilane: (3-chloropropyl) trimethoxysilane diaminosilane: N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane Phenylsilane: phenyltrimethoxysilane (molecular weight 240.4) Alkylsilane: n-propyltrimethoxysilane (molecular weight 164.3)
  • phenyltrimethoxysilane and n-propyltrimethoxysilane do not have any functional groups included in functional group groups A and B.
  • a glass fiber woven fabric (warp weave density: 29 yarns / 25 mm, weft weave density: 32 yarns / 25 mm) using glass fiber synthetic twisted yarn (135Tex) as warp yarns and weft yarns is glass fiber woven fabric 2; 2 using a laminate in which a surface treatment layer containing a urethane resin as a coating agent and not containing a silane coupling agent is formed on the surface of 2 and 3 as a first silane coupling agent S1 on the surface of the laminate Forming a first surface treatment layer 3 containing a mixed silane coupling agent in which an aminopropyltriethoxysilane and 3-methacryloxypropyltrimethoxysilane are mixed in a mass ratio of 46.9: 53.1, The second surface treatment layer 4 containing the silane coupling agent S2 was not formed at all, and the preparation of the surface-treated glass fiber woven / knitted fabric 1 was tried.
  • the mixed silane coupling agent produced a cloudy precipitate due to the reaction between 3-aminopropyltriethoxysilane and 3-methacryloxypropyltrimethoxysilane, and uniform surface treatment could not be performed.
  • the silicone resin layer 5 is formed on the first surface treated layer 3 of the surface treated glass fiber woven and knitted fabric 1 in the same manner as in Examples 1 to 12, the silicone of the surface treated glass fiber woven and knitted fabric 1 is The adhesive strength to the resin layer 5 could not be appropriately evaluated. The results are shown in Table 4.
  • a glass fiber woven fabric (warp weave density: 29 yarns / 25 mm, weft weave density: 32 yarns / 25 mm) having glass fiber twisted yarn (135Tex) as warp yarns and weft yarns is used as the glass fiber woven fabric 2; Using a laminate on the surface of which a surface treatment layer containing a urethane resin as a coating agent and not containing a silane coupling agent is formed, and heat-treating the laminate at a temperature of 400 ° C. for 54 hours; The surface treatment layer was removed.
  • a glass fiber reinforced silicone resin film material 6 was produced by forming a silicone resin layer 5 on the glass fiber woven and knitted fabric 2 from which the surface treatment layer has been removed in the same manner as in Examples 1 to 12. .
  • the first silane coupling agent has a first functional group selected from the functional group group A
  • the second silane coupling agent is the functional group group.
  • B has a second functional group selected from B
  • the first silane coupling agent has a first functional group selected from the functional group B
  • the second silane coupling Agent has a second functional group selected from the functional group group A
  • the mass of the second silane coupling agent is 80% by mass or more of the mass of the entire second surface treatment layer 4
  • the first silane coupling agent has a first functional group selected from the functional group group A or the functional group group B, and the second silane cup Comparison in which the ring agent has a second functional group selected from the same functional group as the first functional group, or has a functional group which is not contained in either the functional group A or the functional group B
  • the surface-treated glass fiber woven or knitted fabric 1 of Examples 1 to 6 it is apparent that the surface-treated glass fiber woven or knitted fabric 1 can not obtain sufficient adhesive strength to the silicone resin layer 5.
  • the second silane coupling agent may have a first functional group selected from the functional group group A, and the second silane coupling agent may have a second functional group selected from the functional group group B.
  • the mass of the second silane coupling agent is less than 80% by mass of the mass of the entire second surface-treated layer, It is apparent that the surface-treated glass fiber woven / knit 1 can not obtain sufficient adhesive strength to the silicone resin layer 5.

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Abstract

Provided are: surface-treated, woven or knit glass fiber fabric capable of attaining high strength of adhesion to silicone resin layers; and a glass-fiber-reinforced silicone resin film material having excellent mechanical strength. The surface-treated, woven or knit glass fiber fabric 1 comprises woven or knit glass fiber fabric 2 and, disposed over a surface thereof, a first surface treatment layer 3, which comprises a first silane coupling agent, and a second surface treatment layer 4, which comprises a second silane coupling agent. The first silane coupling agent has a first functional group selected from among either functional groups A or functional groups B. The second silane coupling agent has a second functional group, which is selected from among functional groups differing from the functional groups to which the first functional group belongs. The second silane coupling agent accounts for 80 mass% or more of the total mass of the second surface treatment layer.

Description

表面処理ガラス繊維織編物及びそれを用いるガラス繊維強化シリコーン樹脂膜材Surface-treated glass fiber woven or knitted fabric and glass fiber reinforced silicone resin film material using the same
　本発明は、表面処理ガラス繊維織編物及びそれを用いるガラス繊維強化シリコーン樹脂膜材に関する。 The present invention relates to a surface-treated glass fiber woven or knitted fabric and a glass fiber-reinforced silicone resin film material using the same.
　ガラス繊維織物又はガラス繊維編物の上にシリコーン樹脂層を設け、ガラス繊維強化シリコーン樹脂膜材を形成することが検討されている。尚、本願では前記ガラス繊維織物と前記ガラス繊維編物とを合わせて「ガラス繊維織編物」という。 It has been studied to provide a silicone resin layer on a glass fiber woven fabric or a glass fiber knitted fabric to form a glass fiber reinforced silicone resin film material. In the present application, the glass fiber woven fabric and the glass fiber knitted fabric are collectively referred to as "glass fiber woven and knitted fabric".
　ガラス繊維織編物上に樹脂層を設ける場合、樹脂に対する親和性を付与するために、ガラス繊維の表面にシランカップリング剤からなるコーティング層を形成し、表面処理ガラス繊維織編物とすることが行われている。また、ガラス繊維の表面にシランカップリング剤からなるコーティング層を形成する場合、コーティング層を２層とすることが知られている（例えば、特許文献１参照）。 When providing a resin layer on a glass fiber woven or knitted fabric, in order to impart affinity to the resin, a coating layer consisting of a silane coupling agent is formed on the surface of the glass fiber to form a surface treated glass fiber woven or knitted fabric. It is Moreover, when forming the coating layer which consists of a silane coupling agent on the surface of glass fiber, it is known to make a coating layer into two layers (for example, refer patent document 1).
特許第５８４４５０１号公報Patent No. 5845501 gazette
　しかしながら、ガラス繊維の表面にシランカップリング剤からなるコーティング層を２層設ける場合、それぞれのコーティング層を形成するシランカップリング剤の組合せによっては、該コーティング層を備える表面処理ガラス繊維織編物の最表面のコーティング層上に設けるシリコーン樹脂層に対して十分な接着強度を得ることができず、得られたガラス繊維強化シリコーン樹脂膜材においても十分な機械的強度を得ることができないという不都合がある。 However, when two coating layers consisting of a silane coupling agent are provided on the surface of the glass fiber, depending on the combination of the silane coupling agent forming each coating layer, the most surface-treated glass fiber woven or knitted fabric provided with the coating layer There is a disadvantage that sufficient adhesive strength can not be obtained with respect to the silicone resin layer provided on the surface coating layer, and sufficient mechanical strength can not be obtained even in the obtained glass fiber reinforced silicone resin film material .
　本発明は、かかる不都合を解消して、シリコーン樹脂層に対して強固な接着強度を得ることができる表面処理ガラス繊維織編物を提供することを目的とする。 An object of the present invention is to provide a surface-treated glass fiber woven or knitted fabric which can eliminate such disadvantages and obtain strong adhesive strength to a silicone resin layer.
　また、本発明の目的は、優れた機械的強度を備えるガラス繊維強化シリコーン樹脂膜材を提供することにもある。 Another object of the present invention is to provide a glass fiber reinforced silicone resin film material having excellent mechanical strength.
　かかる目的を達成するために、本発明の表面処理ガラス繊維織編物は、ガラス繊維織編物表面に、第１のシランカップリング剤及び被膜剤を含む第１の表面処理層と、第２のシランカップリング剤を含む第２の表面処理層とをこの順に備える表面処理ガラス繊維織編物であって、前記第１のシランカップリング剤は、第１級アミノ基及び第２級アミノ基からなる官能基群Ａ、又は末端ビニル基、末端エポキシ基及び末端ハロゲノ基からなる官能基群Ｂのいずれかの群から選択される１つの官能基である第１の官能基を有し、前記第２のシランカップリング剤は、前記第１の官能基が属する前記官能基群とは異なる官能基群から選択される１つの官能基である第２の官能基を有し、前記第２のシランカップリング剤の質量は、前記第２の表面処理層全体の質量の８０質量％以上であることを特徴とする。 In order to achieve such an object, the surface-treated glass fiber woven or knitted fabric of the present invention comprises a first surface treated layer comprising a first silane coupling agent and a coating agent on the glass fiber woven / knitted surface, and a second silane. A surface-treated glass fiber woven or knitted fabric comprising a second surface-treated layer containing a coupling agent in this order, wherein the first silane coupling agent is a functional group consisting of a primary amino group and a secondary amino group A second functional group having a first functional group which is one functional group selected from any group of group group A or functional group group B consisting of a terminal vinyl group, a terminal epoxy group and a terminal halogeno group; The silane coupling agent has a second functional group which is one functional group selected from functional group groups different from the functional group group to which the first functional group belongs, and the second silane coupling The mass of the agent is said second surface Characterized in that at least 80 wt% of the total mass physical layer.
　本発明の表面処理ガラス繊維織編物は、ガラス繊維織編物表面に、第１のシランカップリング剤及び被膜剤を含む第１の表面処理層と、第２のシランカップリング剤を含む第２の表面処理層とをこの順に備える。 The surface-treated glass fiber woven or knitted fabric of the present invention comprises a first surface-treated layer containing a first silane coupling agent and a coating agent, and a second surface-treated layer containing a second silane coupling agent on the glass fiber woven / knitted surface. A surface treatment layer is provided in this order.
　このとき、前記第１のシランカップリング剤は、第１級アミノ基及び第２級アミノ基からなる官能基群Ａ、又は末端ビニル基、末端エポキシ基及び末端ハロゲノ基からなる官能基群Ｂのいずれかの群から選択される１つの官能基である第１の官能基を有する。一方、前記第２のシランカップリング剤は、前記第１の官能基が選択された前記官能基群とは異なる官能基群から選択される１つの官能基である第２の官能基を有する。 At this time, the first silane coupling agent is a functional group group A consisting of a primary amino group and a secondary amino group, or a functional group group B consisting of a terminal vinyl group, a terminal epoxy group and a terminal halogeno group. It has a first functional group which is one functional group selected from any group. On the other hand, the second silane coupling agent has a second functional group which is one functional group selected from functional group groups different from the functional group group from which the first functional group is selected.
　すなわち、前記第１のシランカップリング剤が前記官能基群Ａから選択された第１の官能基を有する場合には、前記第２のシランカップリング剤は前記官能基群Ｂから選択された第２の官能基を有する。また、前記第１のシランカップリング剤が前記官能基群Ｂから選択された第１の官能基を有する場合には、前記第２のシランカップリング剤は前記官能基群Ａから選択された第２の官能基を有する。 That is, when the first silane coupling agent has a first functional group selected from the functional group group A, the second silane coupling agent is selected from the functional group group B. It has 2 functional groups. When the first silane coupling agent has a first functional group selected from the functional group group B, the second silane coupling agent is selected from the functional group group A. It has 2 functional groups.
　本発明の表面処理ガラス繊維織編物は、前記構成に加え、前記第２のシランカップリング剤の質量が、前記第２の表面処理層全体の質量の８０質量％以上であることにより、該第２の表面処理層上にシリコーン樹脂層を設けたときに、該シリコーン樹脂層に対して強固な接着強度を得ることができ、さらに得られたガラス繊維強化シリコーン樹脂膜材において優れた機械的強度を得ることができる。 In the surface-treated glass fiber woven or knitted fabric of the present invention, the mass of the second silane coupling agent is 80% by mass or more of the mass of the entire second surface-treated layer, in addition to the above configuration. When a silicone resin layer is provided on the surface treatment layer of 2, the adhesive strength strong against the silicone resin layer can be obtained, and the mechanical strength is excellent in the obtained glass fiber reinforced silicone resin film material. You can get
　本発明の表面処理ガラス繊維織編物は、前記第１の表面処理層と前記第２の表面処理層とが前述の構成を備える場合以外には、該第２の表面処理層上に設けられた前記シリコーン樹脂層に対して十分な接着強度を得ることができない。また、本発明の表面処理ガラス繊維織編物は、前記第２のシランカップリング剤の質量が、前記第２の表面処理層全体の質量の８０質量％未満であるときには、前記第１の表面処理層と前記第２の表面処理層との構成に関わらず、該第２の表面処理層上に設けられた前記シリコーン樹脂層に対して十分な接着強度を得ることができない。 The surface-treated glass fiber woven or knitted fabric according to the present invention is provided on the second surface-treated layer except when the first surface-treated layer and the second surface-treated layer have the above-described configuration. Sufficient adhesive strength can not be obtained for the silicone resin layer. In the surface-treated glass fiber woven or knitted fabric of the present invention, when the mass of the second silane coupling agent is less than 80% by mass of the mass of the entire second surface-treated layer, the first surface treatment Regardless of the configuration of the layer and the second surface treatment layer, sufficient adhesive strength can not be obtained for the silicone resin layer provided on the second surface treatment layer.
　また、本発明の表面処理ガラス繊維織編物においては、前記官能基群Ａが末端第１級アミノ基からなり、前記官能基群Ｂが末端メタクリロイル基、末端グリシドキシ基及びクロロ基からなることが好ましい。この結果、本発明の表面処理ガラス繊維織編物は、前記第２の表面処理層上に設けられた前記シリコーン樹脂層に対してより強固な接着強度を得ることができる。 Further, in the surface-treated glass fiber woven or knitted fabric of the present invention, it is preferable that the functional group group A comprises a terminal primary amino group, and the functional group group B comprises a terminal methacryloyl group, a terminal glycidoxy group and a chloro group. . As a result, the surface-treated glass fiber woven or knitted fabric of the present invention can obtain stronger adhesive strength to the silicone resin layer provided on the second surface-treated layer.
　また、本発明の表面処理ガラス繊維織編物においては、前記第１のシランカップリング剤と前記第２のシランカップリング剤とのモル比が、７０：３０～１３：８７の範囲であることが好ましい。この結果、本発明の表面処理ガラス繊維織編物は、前記第２の表面処理層上に設けられた前記シリコーン樹脂層に対してさらに強固な接着強度を得ることができる。 In the surface-treated glass fiber woven or knitted fabric of the present invention, the molar ratio of the first silane coupling agent to the second silane coupling agent is in the range of 70:30 to 13:87. preferable. As a result, the surface-treated glass fiber woven or knitted fabric of the present invention can obtain stronger adhesive strength to the silicone resin layer provided on the second surface-treated layer.
　また、本発明の表面処理ガラス繊維織編物においては、経方向及び緯方向の引張強さが、１５００Ｎ／２５ｍｍ以上であることが好ましい。この結果、本発明の表面処理ガラス繊維織編物を用いることで、優れた強度を備えるガラス繊維強化シリコーン樹脂膜材を得ることができる。 Moreover, in the surface-treated glass fiber woven or knitted fabric of the present invention, it is preferable that the tensile strength in the warp direction and the weft direction is 1500 N / 25 mm or more. As a result, by using the surface-treated glass fiber woven or knitted fabric of the present invention, it is possible to obtain a glass fiber reinforced silicone resin membrane material having excellent strength.
　さらに、本発明の表面処理ガラス繊維織編物においては、前記第１の官能基と前記第２の官能基とが化学結合を形成していることが好ましい。前記第１の官能基と前記第２の官能基とが化学結合を形成すると、第２のシランカップリング剤に含まれるアルコキシ基が加水分解を受けてシラノール基が生成し、該シラノール基が、第２の表面処理層の第１の表面処理層と接しない表面に存在することになるので、前記第２の表面処理層上に設けられた前記シリコーン樹脂層に対する接着強度を向上する点で好ましい。 Furthermore, in the surface-treated glass fiber woven or knitted fabric of the present invention, it is preferable that the first functional group and the second functional group form a chemical bond. When the first functional group and the second functional group form a chemical bond, the alkoxy group contained in the second silane coupling agent is hydrolyzed to form a silanol group, and the silanol group is Since it exists on the surface not in contact with the first surface treatment layer of the second surface treatment layer, it is preferable from the viewpoint of improving the adhesive strength to the silicone resin layer provided on the second surface treatment layer. .
　本発明のガラス繊維強化シリコーン樹脂膜材は、前記いずれかの構成を備える本発明の表面処理ガラス繊維織編物の前記第２の表面処理層上に、シリコーン樹脂層を備えることにより、優れた機械的強度を得ることができる。 The glass fiber reinforced silicone resin membrane material of the present invention is an excellent machine by providing the silicone resin layer on the second surface treated layer of the surface treated glass fiber woven or knitted fabric of the present invention having any of the above-mentioned constitutions. Strength can be obtained.
本発明の表面処理ガラス繊維織編物の構成を示す説明的断面図。Explanatory sectional drawing which shows the structure of the surface-treated glass fiber woven knitted fabric of this invention.
　次に、添付の図面を参照しながら、本発明の実施の形態についてさらに詳しく説明する。 Embodiments of the present invention will now be described in more detail with reference to the accompanying drawings.
　図１に示すように、本実施形態の表面処理ガラス繊維織編物１は、ガラス繊維織編物２表面に、第１のシランカップリング剤及び被膜剤を含む第１の表面処理層３と、第２のシランカップリング剤を含む第２の表面処理層４とをこの順に備える。そして、表面処理ガラス繊維織編物１は、第２の表面処理層４上にシリコーン樹脂層５が設けられることによりガラス繊維強化シリコーン樹脂膜材６を形成する。 As shown in FIG. 1, the surface-treated glass fiber woven or knitted fabric 1 of the present embodiment comprises a first surface treated layer 3 containing a first silane coupling agent and a coating agent on the surface of the glass fiber woven or knitted fabric 2; And a second surface treatment layer 4 containing two silane coupling agents in this order. The surface-treated glass fiber woven or knitted fabric 1 forms the glass fiber-reinforced silicone resin film material 6 by providing the silicone resin layer 5 on the second surface-treated layer 4.
　前記ガラス繊維織編物１は、ガラス繊維織物であってもよく、ガラス繊維編物であってもよい。前記ガラス繊維織物としては、例えば、フィラメント径が３～１０μｍのガラスフィラメントが５０～２５００本集束されてなる、重量１．５～１５０ｔｅｘの無撚糸、無撚糸に撚りを掛けた撚糸、又は、複数本の無撚糸又は撚糸を撚り合わせてなる合撚糸を、経糸及び緯糸として、２０本／２５ｍｍ～１００本／２５ｍｍの織密度で、平織、綾織、朱子織、畦織等してなる、厚さ０．１～１．０ｍｍ、単位面積当たりの質量１０～２０００ｇ／ｍ２のガラス繊維織物を挙げることができる。また、前記ガラス繊維編物としては、例えば、フィラメント径が３～１０μｍのガラスフィラメントが５０～２５００本集束されてなる、重量１．５～１５０ｔｅｘの無撚糸、無撚糸に撚りを掛けた撚糸、又は、複数本の無撚糸又は撚糸を撚り合わせてなる合撚糸を、編糸として、トリコット編み、ラッセル編み等をして得られたガラス繊維編物を挙げることができる。高い引張強度が得られることから、本実施形態の表面処理ガラス繊維織編物１には、ガラス繊維織物を用いることが好ましい。 The glass fiber woven or knitted fabric 1 may be a glass fiber woven fabric or a glass fiber woven fabric. As the glass fiber woven fabric, for example, an untwisted yarn having a weight of 1.5 to 150 tex, a twisted yarn obtained by twisting an untwisted yarn, or a plurality of 50 to 2500 glass filaments having a filament diameter of 3 to 10 μm are collected. A double-twisted yarn formed by twisting together untwisted yarns or twisted yarns of the present invention as a warp yarn and weft, with a weave density of 20 yarns / 25 mm to 100 yarns / 25 mm, plain weave, twill weave, satin weave, twill weave, etc. A glass fiber woven fabric having a weight of 10 to 2000 g / m 2 per unit area can be mentioned. Further, as the glass fiber knitted fabric, for example, an untwisted yarn having a weight of 1.5 to 150 tex, a twisted yarn obtained by twisting an untwisted yarn, or 50 to 2,500 glass filaments having a filament diameter of 3 to 10 μm are collected. As a knitting yarn, a glass fiber knitted fabric obtained by tricot knitting, Russell knitting, etc. can be mentioned as a knitting yarn, which is formed by twisting together a plurality of non-twist yarns or twist yarns. Since high tensile strength is obtained, it is preferable to use a glass fiber woven fabric for the surface-treated glass fiber woven or knitted fabric 1 of the present embodiment.
　前記シリコーン樹脂層５を形成するシリコーン樹脂としては、例えば、付加反応硬化型シリコーンエラストマー、縮合反応硬化型シリコーンエラストマー等、柔軟性を有するシリコーン樹脂を挙げることができる。 As a silicone resin which forms the said silicone resin layer 5, the silicone resin which has a softness | flexibility, such as an addition reaction curing type silicone elastomer, a condensation reaction curing type silicone elastomer, can be mentioned, for example.
　前記第１の表面処理層３に含まれる前記第１のシランカップリング剤は、第１級アミノ基及び第２級アミノ基からなる官能基群Ａ、又は末端ビニル基、末端エポキシ基及び末端ハロゲノ基からなる官能基群Ｂのいずれかの群から選択される１つの官能基である第１の官能基を有する。また、前記第２の表面処理層４に含まれる前記第２のシランカップリング剤は、前記第１の官能基が選択された前記官能基群とは異なる官能基群から選択される１つの官能基である第２の官能基を有する。 The first silane coupling agent contained in the first surface treatment layer 3 is a functional group group A consisting of a primary amino group and a secondary amino group, or a terminal vinyl group, a terminal epoxy group and a terminal halogeno. It has a first functional group which is one functional group selected from any group of functional group group B consisting of groups. In addition, the second silane coupling agent contained in the second surface treatment layer 4 is one functional group selected from functional group groups different from the functional group group from which the first functional group is selected. It has a second functional group which is a group.
　本実施形態では、前記第１のシランカップリング剤が前記官能基群Ａから選択された第１の官能基を有する場合には、前記第２のシランカップリング剤は前記官能基群Ｂから選択された第２の官能基を有する。また、前記第１のシランカップリング剤が前記官能基群Ｂから選択された第１の官能基を有する場合には、前記第２のシランカップリング剤は前記官能基群Ａから選択された第２の官能基を有する。 In the present embodiment, when the first silane coupling agent has a first functional group selected from the functional group group A, the second silane coupling agent is selected from the functional group group B. Having a second functional group. When the first silane coupling agent has a first functional group selected from the functional group group B, the second silane coupling agent is selected from the functional group group A. It has 2 functional groups.
　前記第１級アミノ基を有するシランカップリング剤としては、例えば、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－（２－アミノエチル）アミノプロピルトリメトキシシラン、ウレイドプロピルトリメトキシシラン、ウレイドプロピルトリエトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン等を挙げることができるが、末端第１級アミノ基を有する３－アミノプロピルトリエトキシシラン（分子量２２１．４）又はＮ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン（分子量２２２．４）を好適に用いることができる。 Examples of the silane coupling agent having a primary amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, and ureidopropyltriol. Examples include methoxysilane, ureidopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane. Preferably, 3-aminopropyltriethoxysilane (molecular weight 221.4) or N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (molecular weight 222.4) having a terminal primary amino group is preferably used. it can.
　前記第２級アミノ基を有するシランカップリング剤としては、例えば、Ｎ－（ビニルベンジル－２－アミノエチル－３－アミノプロピルトリメトキシシラン塩酸塩、３－（２－アミノエチル）アミノプロピルトリメトキシシラン、３－フェニルアミノプロピルトリメトキシシラン、ウレイドプロピルトリメトキシシラン、ウレイドプロピルトリエトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン等を挙げることができるが、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン（分子量２２２．４）又はＮ－（ビニルベンジル－２－アミノエチル－３－アミノプロピルトリメトキシシラン塩酸塩（分子量３７５）を好適に用いることができる。 Examples of the silane coupling agent having a secondary amino group include N- (vinylbenzyl-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3- (2-aminoethyl) aminopropyltrimethoxy. Silane, 3-phenylaminopropyltrimethoxysilane, ureidopropyltrimethoxysilane, ureidopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3 N- (aminoethyl) -3-aminopropyltrimethoxysilane (molecular weight 222.4) or N- (vinylbenzyl-2-aminoethyl-3-). Aminopropyltrimethoxysilane hydrochloride (molecular weight 375) It can be suitably used.
　前記末端ビニル基を有するシランカップリング剤としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルアセトキシシラン、アリルトリメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－アクリロキシプロピルトリメトキシシラン、Ｎ－（ビニルベンジル）－２－アミノエチル－３－アミノプロピルトリメトキシシラン塩酸塩等を挙げることができるが、ビニルメトキシシラン（分子量１４８．２）、Ｎ－（ビニルベンジル）－２－アミノエチル－３－アミノプロピルトリメトキシシラン塩酸塩（分子量３７５）、３－アクリロキシプロピルトリメトキシシラン（分子量２３４．３）を好適に用いることができ、末端メタクリロイル基を有する３－メタクリロキシプロピルトリメトキシシラン（分子量２４８．４）をさらに好適に用いることができる。 Examples of the silane coupling agent having a terminal vinyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinylacetoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxy Silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride And the like, but vinyl methoxysilane (molecular weight 148.2), N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl trimethoxysilane hydrochloride (molecular weight 375), 3-acrylic Trimethoxysilane (molecular weight 234.3) can be preferably used, having a terminal methacryloyl group 3-methacryloxypropyltrimethoxysilane a trimethoxy silane (molecular weight 248.4) can be further suitably used.
　前記末端エポキシ基を有するシランカップリング剤としては、例えば、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン等を挙げることができるが、末端グリシドキシ基を有する３－グリシドキシプロピルトリメトキシシラン（分子量２３４．３）を好適に用いることができる。 Examples of the silane coupling agent having a terminal epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxy Propylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. may be mentioned, but 3-glycidoxypropyltrimethoxysilane (molecular weight 234.3) having a terminal glycidoxy group is preferred. It can be used for
　前記末端ハロゲノ基を有するシランカップリング剤としては、例えば、（３－クロロプロピル）トリメトキシシラン、（３－クロロプロピル）トリエトキシシラン等を挙げることができるが、末端クロロ基を有する（３－クロロプロピル）トリメトキシシランを好適に用いることができる。 Examples of the silane coupling agent having a terminal halogeno group include (3-chloropropyl) trimethoxysilane, (3-chloropropyl) triethoxysilane, etc. Chloropropyl) trimethoxysilane can be preferably used.
　また、前記第１のシランカップリング剤と共に前記第１の表面処理層３に含まれる被膜剤としては、例えば、ウレタン樹脂、エポキシ樹脂、アクリル樹脂、酢酸ビニル樹脂、ポリエステル樹脂等を挙げることができる。なお、前記第１の表面処理層３は、前記第２の表面処理層４の前記シリコーン樹脂層５に対する接着強度が向上するという理由により前記被膜剤としてデンプンを含まないことが好ましい。 Moreover, as a film agent contained in the said 1st surface treatment layer 3 with the said 1st silane coupling agent, a urethane resin, an epoxy resin, an acrylic resin, a vinyl acetate resin, polyester resin etc. can be mentioned, for example. . Preferably, the first surface treatment layer 3 does not contain starch as the coating agent because the adhesion strength of the second surface treatment layer 4 to the silicone resin layer 5 is improved.
　また、本実施形態では、前記第１のシランカップリング剤の質量は、前記第１の表面処理層３全体の質量の、例えば０．５～１０質量％の範囲とすることができ、好ましくは０．８～８．０質量％、より好ましくは１．０～５．０質量％の範囲とすることができる。 Further, in the present embodiment, the mass of the first silane coupling agent can be, for example, in the range of 0.5 to 10 mass% of the mass of the entire first surface treatment layer 3, and preferably The content can be in the range of 0.8 to 8.0% by mass, more preferably 1.0 to 5.0% by mass.
　一方、前記第２のシランカップリング剤の質量は、前記第２の表面処理層４全体の質量の８０質量％以上であることが必要であり、好ましくは９０質量％以上、より好ましくは９５質量％以上、さらに好ましくは９９質量％以上であり、特に好ましくは該第２の表面処理層４は実質的に該第２のシランカップリング剤のみで構成される。 On the other hand, the mass of the second silane coupling agent is required to be 80 mass% or more of the mass of the entire second surface treatment layer 4, preferably 90 mass% or more, more preferably 95 mass % Or more, more preferably 99% by mass or more, and particularly preferably, the second surface treatment layer 4 is substantially composed of only the second silane coupling agent.
　第２の表面処理層４は、シリコーン樹脂層５に対する接着強度を低下させるおそれがあることから、無機粒子、例えば、顔料、を含まないことが好ましい。 The second surface treatment layer 4 preferably does not contain inorganic particles, for example, a pigment, because the second surface treatment layer 4 may reduce the adhesive strength to the silicone resin layer 5.
　前記第１のシランカップリング剤及び前記第２のシランカップリング剤の合計質量は、前記第１の表面処理層３全体及び前記第２の表面処理層４全体の合計質量の、例えば１．０～３５．０質量％の範囲とすることができ、好ましくは２．０～３０．０質量％、より好ましくは５．０～２０．０質量％、さらに好ましくは５．５～１８．０質量％の範囲とすることができる。 The total mass of the first silane coupling agent and the second silane coupling agent is, for example, 1.0 of the total mass of the entire first surface treatment layer 3 and the entire second surface treatment layer 4. It can be in the range of 3 to 35.0% by mass, preferably 2.0 to 30.0% by mass, more preferably 5.0 to 20.0% by mass, and still more preferably 5.5 to 18.0%. It can be in the range of%.
　また、前記第１のシランカップリング剤及び前記第２のシランカップリング剤の合計質量は、前記表面処理ガラス繊維織編物１全体の質量の、例えば０．０１～０．５０質量％の範囲とすることができ、好ましくは０．０１５～０．１５質量％、より好ましくは０．０２～０．１２質量％の範囲とすることができる。 In addition, the total mass of the first silane coupling agent and the second silane coupling agent is, for example, in the range of 0.01 to 0.50 mass% of the mass of the entire surface-treated glass fiber woven or knitted fabric 1. And preferably in the range of 0.015 to 0.15% by mass, more preferably 0.02 to 0.12% by mass.
　前記第１のシランカップリング剤と前記第２のシランカップリング剤とのモル比は、例えば９６：４～４：９６の範囲とすることができ、前記表面処理ガラス繊維織編物１が前記シリコーン樹脂層５に対して強固な接着強度を得るために、７０：３０～１８：３７の範囲であることが好ましく、６０：４０～１５：８５の範囲であることがより好ましい。 The molar ratio of the first silane coupling agent to the second silane coupling agent can be, for example, in the range of 96: 4 to 4:96, and the surface-treated glass fiber woven or knitted fabric 1 is the silicone. In order to obtain strong adhesive strength to the resin layer 5, the range of 70:30 to 18:37 is preferable, and the range of 60:40 to 15:85 is more preferable.
　また、前記第１のシランカップリング剤と前記第２のシランカップリング剤との重量比は、例えば９６：４～４：９６の範囲とすることができ、７０：３０～１３：８７の範囲であることが好ましく、６０：４０～１２：８８の範囲であることがより好ましい。 The weight ratio of the first silane coupling agent to the second silane coupling agent can be, for example, in the range of 96: 4 to 4:96, and in the range of 70:30 to 13:87. Is preferably, and more preferably in the range of 60:40 to 12:88.
　また、本実施形態では、前記第１の官能基と前記第２の官能基とが化学結合を形成していることが好ましい。前記第１の官能基と前記第２の官能基とが化学結合を形成すると、第２のシランカップリング剤に含まれるアルコキシ基が加水分解を受けてシラノール基が生成し、該シラノール基が、第２の表面処理層４の第１の表面処理層３と接しない表面（シリコーン樹脂層５と接する表面）に存在することになる。前記第２のシランカップリング剤由来のシラノール基は、第２の表面処理層４上にシリコーン樹脂層５が形成されたときに、該シリコーン樹脂層５のシラノール基との間に－Ｓｉ－Ｏ－Ｓｉ－結合を形成することができ、該第２の表面処理層４の該シリコーン樹脂層５に対する接着強度を向上することができるので好ましい。 Furthermore, in the present embodiment, it is preferable that the first functional group and the second functional group form a chemical bond. When the first functional group and the second functional group form a chemical bond, the alkoxy group contained in the second silane coupling agent is hydrolyzed to form a silanol group, and the silanol group is It exists on the surface (surface which contacts silicone resin layer 5) which does not contact with the 1st surface treatment layer 3 of the 2nd surface treatment layer 4. When the silicone resin layer 5 is formed on the second surface treatment layer 4, the silanol group derived from the second silane coupling agent is —Si—O between the silanol group and the silicone resin layer 5. It is preferable because a -Si- bond can be formed, and the adhesive strength of the second surface treatment layer 4 to the silicone resin layer 5 can be improved.
　また、前記ガラス繊維織編物２の表面に、前記第１の表面処理層３と前記第２の表面処理層４とをこの順に備える本実施形態の表面処理ガラス繊維織編物１は、経方向及び緯方向の引張強さが、１５００Ｎ／２５ｍｍ以上であることが好ましい。なお、表面処理ガラス繊維織編物１の経方向及び緯方向の引張強さは、ＪＩＳ　Ｒ　３４２０に準拠して測定する。 In addition, the surface-treated glass fiber woven / knit 1 of the present embodiment in which the first surface-treated layer 3 and the second surface-treated layer 4 are provided in this order on the surface of the glass fiber woven / knit 2 is The tensile strength in the latitudinal direction is preferably 1500 N / 25 mm or more. The tensile strength in the warp direction and in the weft direction of the surface-treated glass fiber woven or knitted fabric 1 is measured in accordance with JIS R 3420.
　ガラス繊維強化シリコーン樹脂膜材６は、本実施形態の表面処理ガラス繊維織編物１に、シリコーン樹脂モノマーを含むペーストを、ナイフコーティングし、熱処理を行うことによりシリコーン樹脂層５を設けることで得ることができる。 The glass fiber reinforced silicone resin film material 6 is obtained by knife-coating a paste containing a silicone resin monomer on the surface-treated glass fiber woven / knitted material 1 of the present embodiment and providing the silicone resin layer 5 by heat treatment. Can.
　次に、本発明の実施例及び比較例を示す。 Next, Examples and Comparative Examples of the present invention will be shown.
　［実施例１～１２］
　まず、表１及び表２に示すように、ガラス繊維合撚糸（１３５Ｔｅｘ）を経糸及び緯糸とするガラス繊維織物（経糸織密度：２９本／２５ｍｍ，緯糸織密度：３２本／２５ｍｍ）をガラス繊維織編物２とし、該ガラス繊維織編物２の表面に、第１のシランカップリング剤Ｓ１を含む第１の表面処理層３を形成した積層体を用い、該積層体の第１の表面処理層３表面に、第２のシランカップリング剤Ｓ２を含む第２の表面処理層４を形成し、表面処理ガラス繊維織編物１を作製した。前記第１の表面処理層３はさらに被膜剤としてウレタン樹脂を含んでいる。なお、第２の表面処理層４に、顔料は含まれない。 [Examples 1 to 12]
First, as shown in Tables 1 and 2, glass fiber woven fabric (warp weave density: 29 yarns / 25 mm, weft weave density: 32 yarns / 25 mm) using glass fiber synthetic twisted yarn (135Tex) as warp yarns and weft yarns The first surface-treated layer of the laminate is formed by using the laminate in which the first surface-treated layer 3 containing the first silane coupling agent S1 is formed on the surface of the woven or knitted fabric 2 and the glass fiber woven / knitted material 2 A second surface treated layer 4 containing a second silane coupling agent S2 was formed on the third surface, and a surface treated glass fiber woven / knitted fabric 1 was produced. The first surface treatment layer 3 further contains a urethane resin as a coating agent. The second surface treatment layer 4 does not contain a pigment.
　次に、前記表面処理ガラス繊維織編物１の前記第２の表面処理層４上に、シリコーン樹脂（信越シリコーン製ＫＥ５６２０Ｗ－Ｕ）を、乾燥後の質量が５０ｇ／ｍ２となるように塗布し、乾燥してシリコーン樹脂層５を形成することにより、ガラス繊維強化シリコーン樹脂膜材６を作製した。 Next, a silicone resin (KE5620W-U made by Shin-Etsu Silicone Co., Ltd.) is applied onto the second surface-treated layer 4 of the surface-treated glass fiber woven / knitted material 1 to a dry weight of 50 g / m 2. The glass fiber reinforced silicone resin film material 6 was produced by drying and forming the silicone resin layer 5.
　次に、社団法人日本膜構造協会試験法標準「膜材料の品質及び性能試験方法」に準拠して、前記表面処理ガラス繊維織編物１の前記シリコーン樹脂層５に対する接着強度を測定した。前記接着強度は、シリコーン樹脂層５が表面処理ガラス繊維織編物１から剥離できず、破損する場合を良好（◎）、シリコーン樹脂層５の一部が表面処理ガラス繊維織編物１に残るが、完全に破損せず、剥離する場合を良（○）、シリコーン樹脂層５が表面処理ガラス繊維織編物１に残らず、完全に剥離する場合を不可（×）として評価した。結果を表１及び表２に示す。 Next, the adhesive strength of the surface-treated glass fiber woven or knitted fabric 1 to the silicone resin layer 5 was measured in accordance with the Japan Membrane Structure Association Test Method Standard “Quality and Performance Test Method of Membrane Material”. The adhesive strength is good when the silicone resin layer 5 can not be peeled off from the surface-treated glass fiber woven / knitted material 1 and damaged (破損), but a part of the silicone resin layer 5 remains on the surface-treated glass fiber woven / woven material 1 The case where the resin was not completely damaged and peeled off was evaluated as good (○), and the case where the silicone resin layer 5 did not remain on the surface-treated glass fiber woven and knitted fabric 1 and completely peeled off was evaluated as unacceptable (×). The results are shown in Tables 1 and 2.
　なお、表１及び表２に記載のシランカップリング剤は次の通りである。 In addition, the silane coupling agent of Table 1 and Table 2 is as follows.
　アミノシラン：３－アミノプロピルトリエトキシシラン
　メタクリルシラン：３－メタクリロキシプロピルトリメトキシシラン
　エポキシシラン：３－グリシドキシプロピルトリメトキシシラン
　クロロシラン：（３－クロロプロピル）トリメトキシシラン
　ジアミノシラン：Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン
　アクリルシラン：３－アクリロキシプロピルトリメトキシシラン
　ビニルシラン：ビニルトリメトキシシラン
　カチオニックシラン：Ｎ－（ビニルベンジル）－２－アミノエチル－３－アミノプロピルトリメトキシシラン塩酸塩
　また、表１～表４における「質量％」は、表面処理層を備えていないガラス繊維のみの質量を１００質量％としたときの値である。 Aminosilane: 3-aminopropyltriethoxysilane methacrylsilane: 3-methacryloxypropyltrimethoxysilane epoxysilane: 3-glycidoxypropyltrimethoxysilane chlorosilane: (3-chloropropyl) trimethoxysilane diaminosilane: N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane acrylsilane: 3-acryloxypropyltrimethoxysilane vinylsilane: vinyltrimethoxysilane Cationic silane: N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl tri Methoxysilane Hydrochloride Further, “mass%” in Tables 1 to 4 is a value when the mass of only the glass fiber not provided with the surface treatment layer is 100 mass%.
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000002
  
Figure JPOXMLDOC01-appb-T000002
  
　［比較例１～７］
　まず、表３に示す第１のシランカップリング剤Ｓ１と、第２のシランカップリング剤Ｓ２とを用いた以外は、実施例１～１２と同様にして、表面処理ガラス繊維織編物１を作製した。前記第１の表面処理層３はさらに被膜剤としてウレタン樹脂を含んでいる。 [Comparative Examples 1 to 7]
First, a surface-treated glass fiber woven or knitted fabric 1 is produced in the same manner as in Examples 1 to 12 except that the first silane coupling agent S1 and the second silane coupling agent S2 shown in Table 3 are used. did. The first surface treatment layer 3 further contains a urethane resin as a coating agent.
　次に、本比較例１～７で得られた前記表面処理ガラス繊維織編物１を用いた以外は、実施例１～１２と同様にして、ガラス繊維強化シリコーン樹脂膜材６を作製した。 Next, a glass fiber reinforced silicone resin film material 6 was produced in the same manner as in Examples 1 to 12 except that the surface-treated glass fiber woven / knitted fabric 1 obtained in Comparative Examples 1 to 7 was used.
　次に、実施例１～１２と同様にして、前記表面処理ガラス繊維織編物１の前記シリコーン樹脂層５に対する接着強度を評価した。結果を表３に示す。 Next, in the same manner as in Examples 1 to 12, the adhesive strength of the surface-treated glass fiber woven or knitted fabric 1 to the silicone resin layer 5 was evaluated. The results are shown in Table 3.
　なお、表３に記載のシランカップリング剤は次の通りである。 In addition, the silane coupling agent of Table 3 is as follows.
　アミノシラン：３－アミノプロピルトリエトキシシラン
　メタクリルシラン：３－メタクリロキシプロピルトリメトキシシラン
　エポキシシラン：３－グリシドキシプロピルトリメトキシシラン
　クロロシラン：（３－クロロプロピル）トリメトキシシラン
　ジアミノシラン：Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン
　フェニルシラン：フェニルトリメトキシシラン（分子量２４０．４）
　アルキルシラン：ｎ－プロピルトリメトキシシラン（分子量１６４．３）
　ここで、フェニルトリメトキシシラン及びｎ－プロピルトリメトキシシランは、官能基群Ａ、Ｂに含まれるいずれの官能基も有していない。 Aminosilane: 3-aminopropyltriethoxysilane methacrylsilane: 3-methacryloxypropyltrimethoxysilane epoxysilane: 3-glycidoxypropyltrimethoxysilane chlorosilane: (3-chloropropyl) trimethoxysilane diaminosilane: N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane Phenylsilane: phenyltrimethoxysilane (molecular weight 240.4)
Alkylsilane: n-propyltrimethoxysilane (molecular weight 164.3)
Here, phenyltrimethoxysilane and n-propyltrimethoxysilane do not have any functional groups included in functional group groups A and B.
Figure JPOXMLDOC01-appb-T000003
  
Figure JPOXMLDOC01-appb-T000003
  
　［比較例８］
　まず、ガラス繊維合撚糸（１３５Ｔｅｘ）を経糸及び緯糸とするガラス繊維織物（経糸織密度：２９本／２５ｍｍ，緯糸織密度：３２本／２５ｍｍ）をガラス繊維織編物２とし、該ガラス繊維織編物２の表面に、被膜剤としてウレタン樹脂を含み、シランカップリング剤を含まない表面処理層が形成された積層体を用い、該積層体の表面に、第１のシランカップリング剤Ｓ１として、３－アミノプロピルトリエトキシシランと３－メタクリロキシプロピルトリメトキシシランとを４６．９：５３．１の質量比で混合した混合シランカップリング剤を含む第１の表面処理層３を形成し、第２のシランカップリング剤Ｓ２を含む第２の表面処理層４は全く形成せずに、表面処理ガラス繊維織編物１の作製を試みた。 Comparative Example 8
First, a glass fiber woven fabric (warp weave density: 29 yarns / 25 mm, weft weave density: 32 yarns / 25 mm) using glass fiber synthetic twisted yarn (135Tex) as warp yarns and weft yarns is glass fiber woven fabric 2; 2 using a laminate in which a surface treatment layer containing a urethane resin as a coating agent and not containing a silane coupling agent is formed on the surface of 2 and 3 as a first silane coupling agent S1 on the surface of the laminate Forming a first surface treatment layer 3 containing a mixed silane coupling agent in which an aminopropyltriethoxysilane and 3-methacryloxypropyltrimethoxysilane are mixed in a mass ratio of 46.9: 53.1, The second surface treatment layer 4 containing the silane coupling agent S2 was not formed at all, and the preparation of the surface-treated glass fiber woven / knitted fabric 1 was tried.
　しかし、前記混合シランカップリング剤は、３－アミノプロピルトリエトキシシランと３－メタクリロキシプロピルトリメトキシシランとの反応により白濁沈殿を生じ、均一な表面処理を行うことができなかった。この結果、表面処理ガラス繊維織編物１の第１の表面処理層３の上に、実施例１～１２と同様にしてシリコーン樹脂層５を形成したときに、表面処理ガラス繊維織編物１のシリコーン樹脂層５に対する接着強度を適切に評価することができなかった。結果を表４に示す。 However, the mixed silane coupling agent produced a cloudy precipitate due to the reaction between 3-aminopropyltriethoxysilane and 3-methacryloxypropyltrimethoxysilane, and uniform surface treatment could not be performed. As a result, when the silicone resin layer 5 is formed on the first surface treated layer 3 of the surface treated glass fiber woven and knitted fabric 1 in the same manner as in Examples 1 to 12, the silicone of the surface treated glass fiber woven and knitted fabric 1 is The adhesive strength to the resin layer 5 could not be appropriately evaluated. The results are shown in Table 4.
　［比較例９］
　まず、ガラス繊維撚糸（１３５Ｔｅｘ）を経糸及び緯糸とするガラス繊維織物（経糸織密度：２９本／２５ｍｍ，緯糸織密度：３２本／２５ｍｍ）をガラス繊維織編物２とし、該ガラス繊維織編物２の表面に、被膜剤としてウレタン樹脂を含み、シランカップリング剤を含まない表面処理層が形成された積層体を用い、該積層体を４００℃の温度で５４時間加熱処理するヒートクリーニングを行い、表面処理層を除去した。次に、前記表面処理層が除去されたガラス繊維織編物２の上に、実施例１～１２と同様にしてシリコーン樹脂層５を形成することにより、ガラス繊維強化シリコーン樹脂膜材６を作製した。 Comparative Example 9
First, a glass fiber woven fabric (warp weave density: 29 yarns / 25 mm, weft weave density: 32 yarns / 25 mm) having glass fiber twisted yarn (135Tex) as warp yarns and weft yarns is used as the glass fiber woven fabric 2; Using a laminate on the surface of which a surface treatment layer containing a urethane resin as a coating agent and not containing a silane coupling agent is formed, and heat-treating the laminate at a temperature of 400 ° C. for 54 hours; The surface treatment layer was removed. Next, a glass fiber reinforced silicone resin film material 6 was produced by forming a silicone resin layer 5 on the glass fiber woven and knitted fabric 2 from which the surface treatment layer has been removed in the same manner as in Examples 1 to 12. .
　得られたガラス繊維強化シリコーン樹脂膜材６では、ガラス繊維織編物２のシリコーン樹脂層５に対する接着強度は良好であったが、前記ヒートクリーニングによりガラス繊維織編物２自体の機械的強度が低下していた。結果を表４に示す。 In the obtained glass fiber reinforced silicone resin film material 6, although the adhesive strength to the silicone resin layer 5 of the glass fiber woven and knitted fabric 2 is good, the mechanical strength of the glass fiber woven and knitted fabric 2 itself is reduced by the heat cleaning. It was The results are shown in Table 4.
Figure JPOXMLDOC01-appb-T000004
  
Figure JPOXMLDOC01-appb-T000004
  
　表１及び表２に示すように、前記第１のシランカップリング剤が前記官能基群Ａから選択された第１の官能基を有し、前記第２のシランカップリング剤が前記官能基群Ｂから選択された第２の官能基を有するか、又は、前記第１のシランカップリング剤が前記官能基群Ｂから選択された第１の官能基を有し、前記第２のシランカップリング剤が前記官能基群Ａから選択された第２の官能基を有し、かつ、前記第２のシランカップリング剤の質量が、前記第２の表面処理層４全体の質量の８０質量％以上である実施例１～１２の表面処理ガラス繊維織編物１によれば、前記シリコーン樹脂層５に対して強固な接着強度を得ることができることが明らかである。 As shown in Tables 1 and 2, the first silane coupling agent has a first functional group selected from the functional group group A, and the second silane coupling agent is the functional group group. B has a second functional group selected from B, or the first silane coupling agent has a first functional group selected from the functional group B, and the second silane coupling Agent has a second functional group selected from the functional group group A, and the mass of the second silane coupling agent is 80% by mass or more of the mass of the entire second surface treatment layer 4 According to the surface-treated glass fiber woven / knitted fabric 1 of Examples 1 to 12, it is apparent that strong adhesive strength can be obtained with respect to the silicone resin layer 5.
　これに対し、表３に示すように、前記第１のシランカップリング剤が前記官能基群Ａ又は前記官能基群Ｂから選択された第１の官能基を有し、前記第２のシランカップリング剤が第１の官能基と同一の官能基群から選択された第２の官能基を有するか、前記官能基群Ａ又は前記官能基群Ｂのいずれにも含まれない官能基を有する比較例１～６の表面処理ガラス繊維織編物１によれば、該表面処理ガラス繊維織編物１が前記シリコーン樹脂層５に対し、十分な接着強度を得ることができないことが明らかである。 On the other hand, as shown in Table 3, the first silane coupling agent has a first functional group selected from the functional group group A or the functional group group B, and the second silane cup Comparison in which the ring agent has a second functional group selected from the same functional group as the first functional group, or has a functional group which is not contained in either the functional group A or the functional group B According to the surface-treated glass fiber woven or knitted fabric 1 of Examples 1 to 6, it is apparent that the surface-treated glass fiber woven or knitted fabric 1 can not obtain sufficient adhesive strength to the silicone resin layer 5.
　また、前記第１のシランカップリング剤が前記官能基群Ａから選択された第１の官能基を有し、前記第２のシランカップリング剤が前記官能基群Ｂから選択された第２の官能基を有するが、前記第２のシランカップリング剤の質量が、前記第２の表面処理層全体の質量の８０質量％未満である比較例７の表面処理ガラス繊維織編物１によれば、該表面処理ガラス繊維織編物１が前記シリコーン樹脂層５に対し、十分な接着強度を得ることができないことが明らかである。 The second silane coupling agent may have a first functional group selected from the functional group group A, and the second silane coupling agent may have a second functional group selected from the functional group group B. According to the surface-treated glass fiber woven / knit 1 of Comparative Example 7, which has a functional group, but the mass of the second silane coupling agent is less than 80% by mass of the mass of the entire second surface-treated layer, It is apparent that the surface-treated glass fiber woven / knit 1 can not obtain sufficient adhesive strength to the silicone resin layer 5.
　また、表４に示すように、３－アミノプロピルトリエトキシシランと３－メタクリロキシプロピルトリメトキシシランとの混合シランカップリング剤のみを用いる比較例８では、ガラス繊維織編物２に対し均一な表面処理を行うことができないことが明らかである。 In addition, as shown in Table 4, in Comparative Example 8 using only a mixed silane coupling agent of 3-aminopropyltriethoxysilane and 3-methacryloxypropyltrimethoxysilane, the surface is uniform with respect to the glass fiber woven and knitted fabric 2 It is clear that no treatment can be done.
　また、ヒートクリーニングを行ったガラス繊維織編物２の表面にシリコーン樹脂層５を形成した比較例９のガラス繊維強化シリコーン樹脂膜材６では、ガラス繊維織編物２自体の機械的強度が低下し、十分な機械的強度を得ることができないことが明らかである。 Further, in the glass fiber reinforced silicone resin membrane material 6 of Comparative Example 9 in which the silicone resin layer 5 is formed on the surface of the glass fiber woven / knitted fabric 2 subjected to heat cleaning, the mechanical strength of the glass fiber woven / knitted fabric 2 itself decreases. It is clear that sufficient mechanical strength can not be obtained.

Claims (6)

  1. 　ガラス繊維織編物表面に、第１のシランカップリング剤及び被膜剤を含む第１の表面処理層と、第２のシランカップリング剤を含む第２の表面処理層とをこの順に備える表面処理ガラス繊維織編物であって、
    　前記第１のシランカップリング剤は、第１級アミノ基及び第２級アミノ基からなる官能基群Ａ、又は末端ビニル基、末端エポキシ基及び末端ハロゲノ基からなる官能基群Ｂのいずれかの群から選択される１つの官能基である第１の官能基を有し、
    　前記第２のシランカップリング剤は、前記第１の官能基が選択された前記官能基群とは異なる官能基群から選択される１つの官能基である第２の官能基を有し、
    　前記第２のシランカップリング剤の質量は、前記第２の表面処理層全体の質量の８０質量％以上であることを特徴とする表面処理ガラス繊維織編物。     Surface-treated glass comprising a first surface-treated layer containing a first silane coupling agent and a coating agent and a second surface-treated layer containing a second silane coupling agent in this order on a glass fiber woven / knitted surface A woven or knitted textile,
    The first silane coupling agent is any of functional group group A consisting of primary amino group and secondary amino group, or functional group group B consisting of terminal vinyl group, terminal epoxy group and terminal halogeno group Having a first functional group which is one functional group selected from the group:
    The second silane coupling agent has a second functional group which is one functional group selected from a functional group different from the functional group from which the first functional group is selected,
    The surface-treated glass fiber woven or knitted fabric, wherein the mass of the second silane coupling agent is 80% by mass or more of the mass of the entire second surface-treated layer.
  2. 　請求項１記載の表面処理ガラス繊維織編物において、前記官能基群Ａが末端第１級アミノ基からなり、前記官能基群Ｂが末端メタクリロイル基、末端グリシドキシ基及びクロロ基からなることを特徴とする表面処理ガラス繊維織編物。 The surface-treated glass fiber woven or knitted fabric according to claim 1, wherein the functional group group A comprises a terminal primary amino group, and the functional group group B comprises a terminal methacryloyl group, a terminal glycidoxy group and a chloro group. Surface-treated glass fiber woven or knitted fabric.
  3. 　請求項１記載の表面処理ガラス繊維織編物において、前記第１のシランカップリング剤と前記第２のシランカップリング剤とのモル比が、７０：３０～１３：８７の範囲であることを特徴とする表面処理ガラス繊維織編物。 The surface-treated glass fiber woven or knitted fabric according to claim 1, wherein the molar ratio of the first silane coupling agent to the second silane coupling agent is in the range of 70:30 to 13:87. Surface-treated glass fiber woven and knitted fabric.
  4. 　請求項１記載の表面処理ガラス繊維織編物において、経方向及び緯方向の引張強さが、１５００Ｎ／２５ｍｍ以上であることを特徴とする表面処理ガラス繊維織編物。 The surface-treated glass fiber woven or knitted fabric according to claim 1, wherein the tensile strength in the warp direction and the latitudinal direction is 1,500 N / 25 mm or more.
  5. 　請求項１記載の表面処理ガラス繊維織編物において、前記第１の官能基と前記第２の官能基とが化学結合を形成していることを特徴とする表面処理ガラス繊維織編物。 The surface-treated glass fiber woven or knitted fabric according to claim 1, wherein the first functional group and the second functional group form a chemical bond.
  6. 　請求項１記載の表面処理ガラス繊維織編物の前記第２の表面処理層上に、シリコーン樹脂層を備えることを特徴とするガラス繊維強化シリコーン樹脂膜材。 A glass fiber reinforced silicone resin film material comprising a silicone resin layer on the second surface treated layer of the surface treated glass fiber woven or knitted fabric according to claim 1.
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