Glass cloth treatment liquid and surface treated glass cloth

Abstract

Provided is a glass cloth treatment liquid in which (A) an organosilicon compound represented by formula (1) and (B) an organosilicon compound represented by formula (2) are dissolved in a water-containing solvent, wherein the concentration of the component (A) is 0.05-2.0 mass%, and the concentration of the component (B) is 0.05-2.0 mass %. (In the formula, R1 represents a hydrogen atom or an alkyl group; R2 represents a hydrogen atom or a methyl group; X represents an oxygen atom or NH; R3 represents a monovalent aliphatic unsaturated hydrocarbon group; m1 and m2 each represent an integer of 1-3; and n1 represents an integer of 1-12.)

Description

Glass cloth treatment liquid and surface-treated glass cloth

[0001] The present invention relates to a glass cloth treatment liquid and a surface-treated glass cloth, and more specifically to a glass cloth treatment liquid containing a (meth)acrylic group-containing organosilicon compound and a carbon-carbon double bond-containing organosilicon compound, and to a surface-treated glass cloth that has been surface-treated with the treatment liquid.

[0002] As information terminals such as smartphones become more powerful and faster, the printed wiring boards they use are becoming increasingly denser and thinner, while also exhibiting lower dielectric constants and lower dielectric loss tangents. A widely used insulating material for these printed wiring boards is a laminated board made by laminating prepregs obtained by impregnating glass cloth with a thermosetting resin (hereinafter referred to as "matrix resin") such as epoxy resin and then curing the prepreg under heat and pressure. Adhesion between the glass cloth and the resin is important for laminates, and insufficient adhesion can lead to delamination at the interface between the glass cloth and the resin during processing or after final product manufacture. Glass cloth is typically treated with a silane coupling agent, which ensures adhesion between the glass cloth and the resin by reacting the organic functional groups of the silane coupling agent with those of the matrix resin. However, conventional silane coupling agents lack sufficient adhesion, and a silane coupling agent with higher adhesion and sufficient stability during processing processes such as etching and long-term reliability was needed.

[0003] A typical silane coupling agent used in glass cloth treatment solutions is 3-methacryloxypropyltrimethoxysilane, as reported in Patent Document 1. However, laminates using glass cloth surface-treated with 3-methacryloxypropyltrimethoxysilane have poor solder heat resistance and alkali resistance, and have had reliability issues.

[0004] International Publication No. 2020 / 194772

[0005] The present invention has been made in view of the above problems, and aims to provide a glass cloth treatment liquid containing a (meth)acrylic group-containing organosilicon compound and an aliphatic unsaturated hydrocarbon group-containing organosilicon compound, glass cloth surface-treated with said glass cloth treatment liquid, and highly reliable prepregs and printed wiring boards.

[0006] The present inventors have conducted extensive research to solve the above problems and have found that a solution of a specific (meth)acrylic group-containing organosilicon compound and a specific aliphatic unsaturated hydrocarbon group-containing organosilicon compound dissolved in a solvent containing water at a specific concentration provides a surface-treated glass cloth that can be used to form highly reliable laminates, thereby completing the present invention.In this specification, the term (meth)acrylic group refers to a methacrylic group or an acrylic group.

[0007] That is, the present invention provides: 1. A glass cloth treatment liquid in which (A) an organosilicon compound represented by the following formula (1) and (B) an organosilicon compound represented by the following formula (2) are dissolved in a solvent containing water, wherein the concentration of component (A) is 0.05 to 2.0 mass %, and the concentration of component (B) is 0.05 to 2.0 mass %. (In the formula, R 1 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R 2 represents a hydrogen atom or a methyl group, Me represents a methyl group, X represents an oxygen atom or NH, R 3 represents a monovalent aliphatic unsaturated hydrocarbon group having 4 to 12 carbon atoms, m1 and m2 each independently represent an integer of 1 to 3, and n1 represents an integer of 1 to 12. 2. In the above formula (1), R 2 3. The glass cloth treatment solution according to 1, wherein R is a methyl group and n1 is 3. 3is a linear or branched alkenyl group having 4 to 8 carbon atoms; 4. The glass cloth treatment liquid according to any one of 1 to 3, wherein the water is adjusted to be acidic; 5. Surface-treated glass cloth the surface of which has been treated with the glass cloth treatment liquid according to 4; 6. A prepreg comprising the surface-treated glass cloth according to 5 and a matrix resin impregnated into the surface-treated glass cloth; and 7. A printed wiring board using the prepreg according to 6.

[0008] The glass cloth treatment liquid of the present invention provides a surface-treated glass cloth that can be suitably used for printed wiring boards and the like, and can improve the productivity during board production and the reliability of the board.

[0009] The present invention will be described in detail below. [Glass Cloth Treatment Liquid] The glass cloth treatment liquid of the present invention (hereinafter sometimes referred to as "treatment liquid") is a glass cloth treatment liquid in which (A) an organosilicon compound represented by the following formula (1) (hereinafter referred to as component (A)) and (B) an organosilicon compound represented by the following formula (2) (hereinafter referred to as component (B)) are dissolved in a solvent containing water.

[0010]

[0011] In formula (1), R 1 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms; R 2 represents a hydrogen atom or a methyl group, Me represents a methyl group, X represents an oxygen atom or NH, R 3 represents a monovalent aliphatic unsaturated hydrocarbon group having 4 to 12 carbon atoms; each m1 independently represents an integer of 1 to 3; and n1 represents an integer of 1 to 12.

[0012] R 1The alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. 1 As the alkyl group, an alkyl group having 1 to 3 carbon atoms is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is even more preferable.

[0013] R 2 is a hydrogen atom or a methyl group, and a methyl group is more preferred.

[0014] X is an oxygen atom or NH, and an oxygen atom is more preferred.

[0015] m1 represents an integer of 1 to 3, preferably 2 or 3, and n1 represents an integer of 1 to 3, more preferably 3 from the viewpoint of raw material procurement.

[0016] Specific examples of the component (A) include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyldimethylmethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropyldimethylethoxysilane, 3-acryloxymethyltrimethoxysilane, 3-acryloxymethylmethyldimethoxysilane, 3-acryloxymethyldimethylmethoxysilane, 3-acryloxymethyltriethoxysilane, 3-acryloxymethylmethyldiethoxysilane, 3-acryloxymethyldimethylethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 3-methacryloxymethyltrimethoxysilane, 3-methacryloxymethylmethyldimethoxysilane, 3-methacryloxymethyldimethylmethoxysilane, 3-methacryloxymethyltriethoxysilane, 3-methacryloxymethylmethyldiethoxysilane, 3-methacryloxymethyldimethylethoxysilane, 3-methacrylamidopropyltrimethoxysilane, 3-methacrylamidopropylmethyldimethoxysilane, 3-methacrylamidopropyldimethylmethoxysilane, 3-methacrylamidopropyltriethoxysilane, 3-methacrylamidopropylmethyldiethoxysilane, 3-methacrylamidopropyldimethylethoxysilane, 3-methacrylamidomethyltrimethoxysilane, 3-methacrylamidomethylmethyldimethoxysilane, 3-methacrylamidomethyldimethylmethoxysilane, 3-methacrylamidomethyltriethoxysilane, 3-methacrylamidomethylmethyldiethoxysilane, 3-methacrylamidomethyldimethylethoxysilane, 3-acrylamidopropyltrimethoxysilane, 3-acrylamidopropylmethyldimethoxysilane, 3-acrylamidopropyldimethylmethoxysilane,Examples of suitable organic silicon compounds include, but are not limited to, 3-acrylamidopropyltriethoxysilane, 3-acrylamidopropylmethyldiethoxysilane, 3-acrylamidopropyldimethylethoxysilane, 3-acrylamidomethyltrimethoxysilane, 3-acrylamidomethylmethyldimethoxysilane, 3-acrylamidomethyldimethylmethoxysilane, 3-acrylamidomethyltriethoxysilane, 3-acrylamidomethylmethyldiethoxysilane, and 3-acrylamidomethyldimethylethoxysilane. Among these, from the viewpoints of ease of availability and water solubility, preferred are organosilicon compounds represented by the following formulas (1-1) to (1-4), more preferred are organosilicon compounds represented by the following formula (1-1) and (1-3), and particularly preferred are organosilicon compounds represented by the following formula (1-3). In the following formulas, Me represents a methyl group, and Et represents an ethyl group.

[0017]

[0018] Component (A) may be commercially available or may be produced by known methods. For example, the organosilicon compound represented by formula (1-1) above and the organosilicon compound represented by formula (1-2) above can be KBM-503 and KBE-503 manufactured by Shin-Etsu Chemical Co., Ltd., respectively. The organosilicon compound represented by formula (1-3) above and the organosilicon compound represented by formula (1-4) above can be obtained, for example, according to the method described in Japanese Patent No. 3,561,501, by reacting methyl methacrylate with an aminoalkylalkoxysilane such as 3-aminopropyltrimethoxysilane in the presence of a polymerization inhibitor and an amidation catalyst at a temperature of about 100 to 200°C.

[0019] The component (A) may be used alone or in combination of two or more.

[0020] The concentration of component (A) in the glass cloth treatment solution of the present invention is 0.05 to 2.0% by mass, preferably 0.1 to 1.0% by mass. If the concentration is less than 0.05% by mass, the amount of silane coupling agent relative to the silanol groups of the glass cloth is insufficient, and the strength of the glass cloth cannot be sufficiently improved. If the concentration exceeds 2.0% by mass, the storage stability of the treatment solution is impaired, and the glass cloth becomes rigid, reducing the productivity of substrate materials.

[0021] On the other hand, in the above formula (2), R 1 Examples of the alkyl group having 1 to 10 carbon atoms include the same as those exemplified above, and an alkyl group having 1 to 3 carbon atoms is preferred, with a methyl group and an ethyl group being more preferred, and a methyl group being even more preferred.

[0022] m2 represents an integer of 1 to 3, with 2 or 3 being preferred.

[0023] R 3 The monovalent aliphatic unsaturated hydrocarbon group having 4 to 12 carbon atoms may be linear, branched, or cyclic, but is preferably a linear or branched alkenyl group having 4 to 8 carbon atoms. Specific examples thereof include 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 3-methyl-2-butenyl, 2-methyl-2-butenyl, 1-ethyl-2-propenyl, propenyl, 2-ethyl-2-propenyl, 1-methyl-4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 5-heptenyl, 6-heptenyl, 1-methyl-6-heptenyl, 1-octenyl, 2-octenyl, 3-octenyl, 4-octenyl, 5-octenyl, 6-octenyl, and 7-octenyl groups.

[0024] Specific examples of the component (B) include 3-butenyltrimethoxysilane, 3-butenylmethyldimethoxysilane, 3-butenyldimethylmethoxysilane, 3-butenyltriethoxysilane, 3-butenylmethyldiethoxysilane, 3-butenyldimethylethoxysilane, 2-butenyltrimethoxysilane, 2-butenylmethyldimethoxysilane, 2-butenyldimethylmethoxysilane, 2-butenyltriethoxysilane, 2-butenylmethyldiethoxysilane, 2-butenyldimethylethoxysilane, 1-butenyltrimethoxysilane, 1-butenylmethyldimethoxysilane, 1-butenyldimethylmethoxysilane, 1-butenyltriethoxysilane, 1-butenylmethyldiethoxysilane, 1-butenyldimethylethoxysilane, 1-methyl-2-propenyltrimethoxysilane, 1-methyl-2-propenylmethyldimethoxysilane, 1-methyl-2-propenyldimethylmethoxysilane, 1-methyl-2-propenyltriethoxysilane, 1-methyl-2-propenylmethyldiethoxysilane, 1-methyl-2-propenyldimethylethoxysilane, 2-methyl-1-propenyltrimethoxysilane, 2-methyl-1-propenylmethyldimethoxysilane, 2-methyl-1-propenyldimethylmethoxysilane, 2-methyl-1-propenyltriethoxysilane, 2-methyl-1-propenylmethyldiethoxysilane, 2-methyl-1-propenyldimethylethoxysilane, 4-pentenyltrimethoxysilane, 4-pentenylmethyldimethoxysilane, 4-pentenyldimethylmethoxysilane, 4-pentenyltriethoxysilane, 4-pentenylmethyldiethoxysilane, 4-pentenyldimethylethoxysilane, 3-pentenyltrimethoxysilane, 3-pentenylmethyldimethoxysilane, 3-pentenyldimethylmethoxysilane, 3-pentenyltriethoxysilane, 3-pentenylmethyldiethoxysilane, 3-pentenyldimethylethoxysilane, 2-pentenyltrimethoxysilane, 2-pentenylmethyldimethoxysilane, 2-pentenyldimethylmethoxysilane, 2-pentenyltriethoxysilane, 2-pentenylmethyldiethoxysilane, 2-pentenyldimethylethoxysilane,1-pentenyltrimethoxysilane, 1-pentenylmethyldimethoxysilane, 1-pentenyldimethylmethoxysilane, 1-pentenyltriethoxysilane, 1-pentenylmethyldiethoxysilane, 1-pentenyldimethylethoxysilane, 1-methyl-3-butenyltrimethoxysilane, 2-methyl-3-butenyltrimethoxysilane, 3-methyl-3-butenyltrimethoxysilane, 1,1-dimethyl-2-propenyltrimethoxysilane, 1,2-dimethyl-2-propenyltrimethoxysilane, 3-methyl-2-butenyltrimethoxysilane, 2-methyl-2-butenyltrimethoxysilane, 1-ethyl-2-propenyltrimethoxysilane, 2-ethyl-2-propenyltrimethoxysilane, 1-methyl-3-butenyltriethoxysilane, 2-methyl-3-butenyltriethoxysilane, 3-methyl-3-butenyltriethoxysilane, 1,1-dimethyl-2-propenyltriethoxysilane, 1,2-dimethyl-2-propenyltriethoxysilane, 3-methyl-2-butenyltriethoxysilane, 2-methyl-2-butenyltriethoxysilane, 1-ethyl-2-propenyltriethoxysilane, 2-ethyl-2-propenyltriethoxysilane, 1-methyl-3-butenylmethyldimethoxysilane, 2-methyl-3-butenylmethyldimethoxysilane, 3-methyl-3-butenylmethyldimethoxysilane, 1,1-dimethyl-2-propenylmethyldimethoxysilane, 1,2-dimethyl-2-propenylmethyldimethoxysilane, 3-methyl-2-butenylmethyldimethoxysilane, 2-methyl-2-butenylmethyldimethoxysilane, 1-ethyl-2-propenylmethyldimethoxysilane, 2-ethyl-2-propenylmethyldimethoxysilane, 1-methyl-4-pentenyltrimethoxysilane, 1-methyl-4-pentenylmethyldimethoxysilane, 1-methyl-4-pentenyldimethylmethoxysilane, 1-methyl-4-pentenyltriethoxysilane, 1-methyl-4-pentenylmethyldiethoxysilane, 1-methyl-4-pentenyldimethylethoxysilane,5-hexenyltrimethoxysilane, 5-hexenylmethyldimethoxysilane, 5-hexenyldimethylmethoxysilane, 5-hexenyltriethoxysilane, 5-hexenylmethyldiethoxysilane, 5-hexenyldimethylethoxysilane, 4-hexenyltrimethoxysilane, 4-hexenylmethyldimethoxysilane, 4-hexenyldimethylmethoxysilane, 4-hexenyltriethoxysilane, 4-hexenylmethyldiethoxysilane, 4-hexenyldimethylethoxysilane, 3-hexenyltrimethoxysilane, 3-hexenylmethyldimethoxysilane, 3-hexenyldimethylmethoxysilane, 3-hexenyltriethoxysilane, 3-hexenylmethyldiethoxysilane, 3-hexenyldimethylethoxysilane, 2-hexenyltrimethoxysilane, 2-hexenylmethyldimethoxysilane, 2-hexenyldimethylmethoxysilane, 2-hexenyltriethoxysilane, 2-hexenylmethyldiethoxysilane, 2-hexenyldimethylethoxysilane, 1-hexenyltrimethoxysilane, 1-hexenylmethyldimethoxysilane, 1-hexenyldimethylmethoxysilane, 1-hexenyltriethoxysilane, 1-hexenylmethyldiethoxysilane, 1-hexenyldimethylethoxysilane, 6-heptenyltrimethoxysilane, 6-heptenylmethyldimethoxysilane, 6-heptenyldimethylmethoxysilane, 6-heptenyltriethoxysilane, 6-heptenylmethyldiethoxysilane, 6-heptenyldimethylethoxysilane, 1-methyl-6-heptenyltrimethoxysilane, 1-methyl-6-heptenylmethyldimethoxysilane, 1-methyl-6-heptenyldimethylmethoxysilane, 1-methyl-6-heptenyltriethoxysilane, 1-methyl-6-heptenylmethyldiethoxysilane, 1-methyl-6-heptenyldimethylethoxysilane, 5-heptenyltrimethoxysilane, 5-heptenylmethyldimethoxysilane, 5-heptenyldimethylmethoxysilane, 5-heptenyltriethoxysilane, 5-heptenylmethyldiethoxysilane, 5-heptenyldimethylethoxysilane,4-heptenyltrimethoxysilane, 4-heptenylmethyldimethoxysilane, 4-heptenyldimethylmethoxysilane, 4-heptenyltriethoxysilane, 4-heptenylmethyldiethoxysilane, 4-heptenyldimethylethoxysilane, 3-heptenyltrimethoxysilane, 3-heptenylmethyldimethoxysilane, 3-heptenyldimethylmethoxysilane, 3-heptenyltriethoxysilane, 3-heptenylmethyldiethoxysilane, 3-heptenyldimethylethoxysilane, 2-heptenyltrimethoxysilane, 2-heptenylmethyldimethoxysilane, 2-heptenyldimethylmethoxysilane, 2-heptenyltriethoxysilane, 2-heptenylmethyldiethoxysilane, 2-heptenyldimethylethoxysilane, 1-heptenyltrimethoxysilane, 1-heptenylmethyldimethoxysilane, 1-heptenyldimethylmethoxysilane, 1-heptenyltriethoxysilane, 1-heptenylmethyldiethoxysilane, 1-heptenyldimethylethoxysilane, 7-octenyltrimethoxysilane, 7-octenylmethyldimethoxysilane, 7-octenyldimethylmethoxysilane, 7-octenyltriethoxysilane, 7-octenylmethyldiethoxysilane, 7-octenyldimethylethoxysilane, 6-octenyltrimethoxysilane, 6-octenylmethyldimethoxysilane, 6-octenyldimethylmethoxysilane, 6-octenyltriethoxysilane, 6-octenylmethyldiethoxysilane, 6-octenyldimethylethoxysilane, 5-octenyltrimethoxysilane, 5-octenylmethyldimethoxysilane, 5-octenyldimethylmethoxysilane, 5-octenyltriethoxysilane, 5-octenylmethyldiethoxysilane, 5-octenyldimethylethoxysilane, 4-octenyltrimethoxysilane, 4-octenylmethyldimethoxysilane, 4-octenyldimethylmethoxysilane, 4-octenyltriethoxysilane, 4-octenylmethyldiethoxysilane, 4-octenyldimethylethoxysilane,Examples of the silane include, but are not limited to, 3-octenyltrimethoxysilane, 3-octenylmethyldimethoxysilane, 3-octenyldimethylmethoxysilane, 3-octenyltriethoxysilane, 3-octenylmethyldiethoxysilane, 3-octenyldimethylethoxysilane, 2-octenyltrimethoxysilane, 2-octenylmethyldimethoxysilane, 2-octenyldimethylmethoxysilane, 2-octenyltriethoxysilane, 2-octenylmethyldiethoxysilane, 2-octenyldimethylethoxysilane, 1-octenyltrimethoxysilane, 1-octenylmethyldimethoxysilane, 1-octenyldimethylmethoxysilane, 1-octenyltriethoxysilane, 1-octenylmethyldiethoxysilane, and 1-octenyldimethylethoxysilane.

[0025] Among these, from the viewpoints of availability and water solubility, organosilicon compounds represented by the following formulae (2-1) to (2-11) are preferred, and organosilicon compounds represented by the following formulae (2-3) to (2-10) are particularly preferred, where Me represents a methyl group.

[0026]

[0027] Component (B) may be commercially available or may be produced by known methods. For example, the organosilicon compound represented by formula (2-10) above and the organosilicon compound represented by formula (2-11) above can be KBM-1063 and KBM-1083, manufactured by Shin-Etsu Chemical Co., Ltd., respectively. The organosilicon compounds represented by formulas (2-3) to (2-9) above can be obtained, for example, by reacting one of the carbon-carbon double bonds of isoprene with a hydrogen atom (Si—H group) bonded to the silicon atom of a hydrosilane such as trimethoxyhydrosilane in the presence of a metal catalyst (hydrosilylation).

[0028] The ratio of isoprene to hydrosilane used in the reaction is not particularly limited, but is preferably 0.4 moles or more and less than 1.5 moles, and more preferably 0.6 moles or more and less than 1.2 moles, of hydrosilane per mole of the isoprene compound.

[0029] The metal catalyst used in the above reaction is not particularly limited, but a platinum compound-containing catalyst or a rhodium compound catalyst is preferred from the viewpoints of availability and reactivity, and a rhodium compound catalyst is more preferred, such as chlorotris(triphenylphosphine)rhodium(I). The reaction temperature is also not particularly limited, and the reaction can be carried out at a temperature from 0°C under heating, but 40 to 110°C is preferred, and the reaction time is usually about 1 to 20 hours.

[0030] The component (B) may be used alone or in combination of two or more. When two or more types are combined, a mixture of the compounds represented by the above formulas (2-3) to (2-9) is preferred.

[0031] The concentration of component (B) in the glass cloth treatment solution of the present invention is 0.05 to 2.0% by mass, preferably 0.1 to 1.0% by mass. If the concentration is less than 0.05% by mass, the amount of silane coupling agent relative to the silanol groups of the glass cloth is insufficient, and the strength of the glass cloth cannot be sufficiently improved. If the concentration exceeds 2.0% by mass, the storage stability of the treatment solution is impaired, and the glass cloth becomes rigid, reducing the productivity of substrate materials.

[0032] The total concentration of components (A) and (B) in the glass cloth treatment liquid of the present invention is preferably 0.1 to 2.5 mass%, more preferably 0.2 to 2.0 mass%, and the mass ratio of components (A) and (B) in the glass cloth treatment liquid of the present invention is preferably 1:10 to 10:1.

[0033] The glass cloth treatment solution of the present invention can be prepared by mixing component (A), component (B), and water and dissolving component (A) and component (B) in water. In this case, component (A) and component (B) may be added to water, or water may be added to a mixture of component (A) and component (B). However, a preferred method is to mix component (A) and component (B) dropwise into water. The temperature during mixing is preferably 10 to 50°C, more preferably 15 to 40°C.

[0034] In addition to components (A) and (B), and water, the glass cloth treatment solution of the present invention may contain an organic solvent to the extent that the effects of the present invention are not impaired. The organic solvent is not particularly limited, but is preferably an organic solvent that is highly compatible with water. Examples include alcohols such as methanol, ethanol, and isopropanol; ethers such as diethyl ether, tetrahydrofuran, and 1,4-dioxane; esters such as ethyl acetate; and ketones such as acetone and methyl ethyl ketone. One organic solvent may be used alone, or two or more organic solvents may be used in combination. When an organic solvent is used, its amount is not particularly limited, but is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass, of the total treatment solution.

[0035] From the viewpoint of stability, it is preferable to use water adjusted to an acidic state in the glass cloth treatment solution of the present invention. Examples of acids used to adjust the acidic state include organic acids such as formic acid, acetic acid, and citric acid, and inorganic acids such as hydrochloric acid. When an acid is used, the amount added is preferably 0.001 to 0.5 mass %, more preferably 0.01 to 0.1 mass %, of the total treatment solution. When an acid is used, water adjusted to an acidic state by mixing the acid with water in advance may be used, or the acid may be added to an aqueous solution containing components (A) and (B) to adjust the acidic state.

[0036] To the glass cloth treatment liquid of the present invention, if necessary, an alkoxy group-containing organosilicon compound, a silazane compound, or the like other than the components (A) and (B) can be added to improve adhesion and bonding to the glass cloth, as long as the effects of the present invention are not impaired. Furthermore, to the glass cloth treatment liquid of the present invention, if necessary, other additives can be added, as long as the effects of the present invention are not impaired. Specific examples of other additives include water-soluble resins, curing catalysts, physical property adjusters that adjust the tensile properties of the resulting cured coating, storage stability improvers, surfactants, metal deactivators, antiozonants, lubricants, pigments, and the like.

[0037] [Surface-treated glass cloth] The surface-treated glass cloth of the present invention is a glass cloth whose surface has been treated with the above-mentioned treatment solution. The surface-treated glass cloth of the present invention can be obtained by applying the glass cloth treatment solution of the present invention to the surface of a glass cloth and, if necessary, drying it by heating.

[0038] [1] Glass Cloth The glass yarns constituting the glass cloth used as the substrate are not particularly limited, and glass yarns of conventionally known glass compositions can be used. Specific examples include E glass, S glass, C glass, D glass, T glass, NE glass, and Q glass (quartz glass), and are appropriately selected depending on the intended use. The form of the glass yarn is also not particularly limited, and examples include filaments, strands obtained by bundling 20 to 400 filaments, and yarns obtained by twisting strands.

[0039] The thickness of the glass cloth is not particularly limited, but is preferably 5 to 300 μm, more preferably 20 to 200 μm, and even more preferably 30 to 150 μm. The mass per unit area is also not particularly limited, but is 10 to 200 g / m. 2 is preferred, and 20 to 150 g / m 2 The weave of the glass cloth is not particularly limited, and examples thereof include plain weave, twill weave, twill weave, satin weave, etc., which are appropriately selected depending on the intended use, and the weave density is also appropriately selected within a conventionally known range.

[0040] [2] Manufacturing method of glass cloth The manufacturing method of the glass cloth used as the substrate is not particularly limited as long as it includes a step of weaving glass yarns, and examples thereof include a method including the following steps: (1) a weaving step of weaving glass yarns to obtain a glass cloth, (2) a fiber-opening step of opening the glass yarns of the glass cloth, and (3) a heat cleaning step of removing the sizing agent attached to the glass yarns of the glass cloth.

[0041] (1) Weaving Process The weaving process is a process in which glass yarns are woven to obtain glass cloth. The weaving method is not particularly limited, and examples thereof include weaving methods using an air jet loom, a water jet loom, a rapier loom, a shuttle loom, etc. When weaving using an air jet loom, etc., PVA or starch can be attached as a secondary sizing agent to obtain further lubricity.

[0042] (2) Fiber-opening process The fiber-opening process is a process of opening the glass fibers of the glass cloth. The fiber-opening method is not particularly limited, but examples thereof include methods of opening the glass fibers using spray water (high-pressure water opening), a vibro washer, ultrasonic water, a mangle, etc.

[0043] (3) Heat Cleaning Process The heat cleaning process is a process for removing sizing agent remaining on the surface of the glass cloth after weaving. When the surface-treated glass cloth is used as a substrate material, the remaining sizing agent undesirably deteriorates the dielectric properties and also leads to insufficient surface treatment of the glass cloth, resulting in poor adhesion with the resin. Heat cleaning methods include methods using flow-type and batch-type heating furnaces. Since the flow-type method burns off the sizing agent all at once at high temperature, which can cause problems such as a decrease in the strength of the glass cloth and residual sizing agent, the batch-type method is generally used, in which organic matter is gradually burned off at 300 to 400°C.

[0044] [3] Method for Surface Treatment of Glass Cloth The method for surface treatment of glass cloth with the glass cloth treatment liquid of the present invention is not particularly limited, and can be carried out, for example, by a method including the following steps: (11) a treatment liquid contact step of contacting the glass cloth surface with the glass cloth treatment liquid of the present invention, and (12) a reaction step of reacting silanol groups on the glass cloth surface with alkoxy groups or silanol groups in the components (A) and (B) contained in the glass cloth treatment liquid of the present invention.

[0045] (11) Treatment Liquid Contacting Step The treatment liquid contacting step is a step of bringing the glass cloth surface into contact with the glass cloth treatment liquid of the present invention. In the treatment liquid contacting step, the contacting method is not particularly limited and may be appropriately selected from known methods, for example, a method of impregnating the glass cloth with the glass cloth treatment liquid of the present invention, a method using roll coating, etc.

[0046] (12) Reaction Step The reaction step is a step in which silanol groups on the glass cloth surface react with alkoxy groups or silanol groups in components (A) and (B) contained in the glass cloth treatment solution of the present invention. The reaction conditions in the reaction step are not particularly limited and can be adjusted appropriately depending on the heat resistance of the glass fiber, the amount of glass cloth treatment solution used, etc. The reaction temperature is preferably 70 to 200°C, more preferably 90 to 150°C. The reaction time is preferably 30 seconds to 30 minutes, more preferably 1 to 20 minutes. Under these conditions, water can be evaporated and the alkoxy groups or silanol groups in components (A) and (B) can react with the silanol groups on the glass cloth surface. The heating method is not particularly limited and can be selected from known methods, such as hot air, infrared rays, and hot rolls.

[0047] In the surface-treated glass cloth of the present invention, the adhesion amounts of components (A) and (B) to the glass cloth substrate are not particularly limited, but from the viewpoints of processability and strength, the adhesion amounts are preferably 0.05 to 0.5 mass%, more preferably 0.05 to 0.2 mass% in total. The adhesion amounts of components (A) and (B) can be measured by the ignition loss method described in JIS R3420:2013.

[0048] The surface-treated glass cloth of the present invention has a cloth mass (g / mm 2 The tensile strength per unit area is preferably 2.1 times or more, more preferably 2.2 times or more, compared to that before the surface treatment. Such a surface-treated glass cloth has excellent processability when made into a prepreg. As will be described later, the tensile strength can be measured in accordance with "7.4 Tensile Strength" of JIS R3420:2013 "General Test Methods for Glass Fibers."

[0049] [Prepreg] The prepreg of the present invention comprises the above-mentioned surface-treated glass cloth and a matrix resin impregnated into the surface-treated glass cloth. The surface-treated glass cloth of the present invention can be made into a prepreg by mixing it with a matrix resin. The prepreg obtained using the surface-treated glass cloth of the present invention has excellent strength and can be suitably used, for example, for printed wiring boards, etc.

[0050] The method for producing the prepreg of the present invention is not particularly limited, and general methods for producing glass cloth-containing substrates, films, prepregs, etc. can be used. For example, a method of impregnating a surface-treated glass cloth with a molten matrix resin or a solution containing a matrix resin can be used. The matrix resin used in the prepreg of the present invention is also not particularly limited, and can be appropriately selected from conventionally known materials, such as thermosetting silicone resins, polyimide resins, maleimide resins, epoxy resins, cyanate resins, (meth)acrylic resins, and polyphenylene ether resins. These resins may be used alone or in combination of two or more. Among these, polyphenylene ether resins are preferred.

[0051] The thickness of the prepreg of the present invention is not particularly limited, but is preferably 10 to 400 μm, more preferably 30 to 300 μm, and even more preferably 40 to 200 μm. Within this range, for example, when the prepreg of the present invention is used for a printed wiring board, a substrate such as a copper-clad laminate can be successfully prepared. The prepreg of the present invention may be semi-cured (B-staged) in advance by heating. The method for B-staging is not particularly limited, but for example, B-staging can be achieved by dissolving the matrix resin in a solvent, impregnating glass cloth with the solution, drying, and then heating at a temperature of 80 to 200°C for 1 to 30 minutes.

[0052] [Printed Wiring Board] The printed wiring board of the present invention is obtained using a prepreg containing the surface-treated glass cloth of the present invention. The method for producing the printed wiring board of the present invention is not particularly limited, and general methods for producing printed circuit boards can be applied. Specific examples include a method in which the prepreg of the present invention is layered on copper foil, pressed, and heat-cured to produce a copper-clad laminate. The method for producing a copper-clad laminate is not particularly limited, but it can be produced, for example, by using 1 to 20 sheets, preferably 2 to 10 sheets, of the above prepreg, placing copper foil on one or both sides of the prepreg, pressing, and heat-curing.

[0053] The thickness of the copper foil is not particularly limited, but is preferably 3 to 70 μm, more preferably 10 to 50 μm, and even more preferably 15 to 40 μm. Within this range, a multilayer copper-clad laminate with high reliability can be formed. The molding conditions for the copper-clad laminate are not particularly limited, but for example, molding can be performed using a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, or the like, at a temperature of 100 to 400°C, a pressure of 1 to 100 MPa, and a heating time of 0.1 to 4 hours. Alternatively, a copper-clad laminate can be formed by combining and molding the prepreg of the present invention, copper foil, and an inner layer wiring board.

[0054] The method of circuit processing is not particularly limited, and examples thereof include circuit formation processing methods such as drilling, metal plating, etching of metal foil, etc. Furthermore, a printed wiring board may be produced by a build-up method in which a composition containing a matrix resin or the prepreg of the present invention and copper foil are sequentially laminated.

[0055] The present invention will be described in more detail below with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to these Examples. In the following formulas, Me represents a methyl group, and Et represents an ethyl group.

[0056] [1] Synthesis of Organosilicon Compound [Synthesis Example 1] With reference to Japanese Patent No. 3561501, an organosilicon compound (1-3) represented by the following formula was obtained.

[0057]

[0058] Synthesis Example 2 A 1-L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer was charged with 0.55 g of chlorotris(triphenylphosphine)rhodium(I), 300.0 g of toluene, 0.3 g of 2,6-di-t-butyl-p-cresol, and 0.1 g of tetrabutylammonium bromide, and 125.4 g (1.84 mol) of isoprene and 150.0 g (1.23 mol) of trimethoxyhydrosilane were added dropwise over 2 hours at an internal temperature of 60 to 70°C. The mixture was then stirred at 60°C for 5 hours, and analyzed by gas chromatography. As a result, it was confirmed that trimethoxyhydrosilane had disappeared. The resulting solution was purified by distillation under conditions of 20 mmHg and 80°C, resulting in a solution with a kinematic viscosity of 1.2 mmHg. 2 180 g of a colorless, transparent liquid having a refractive index of 1.420 was obtained. 1 H-NMR measurement and gas chromatography mass spectrometry (GC / MS) measurement confirmed that the obtained product was a mixture (2) of compounds represented by the following formulas (2-3) to (2-9).

[0059]

[0060] In the above examples, the kinematic viscosity and refractive index were measured at 25°C. In this case, the kinematic viscosity was measured in accordance with JIS Z 8803. The refractive index was measured in accordance with JIS K 0062. Nuclear magnetic resonance spectrum ( 1 H-NMR measurements were performed in deuterated chloroform using an AVANCE III / ULTRASHIELD 400 manufactured by BRUKER. Gas chromatography mass spectrometry (GC / MS) measurements were performed under the following measurement conditions. GC apparatus: 7200 Q-TOF GC / MS manufactured by Agilent Technologies Detector: FID&TTOF-MS Column: HP-5 S-433 (length 30 m x inner diameter 0.25 mm, film thickness 0.25 μm) Column temperature: 50°C → 10°C / min → 280°C (10 minute hold) Injection port temperature: 250°C Detector temperature: 300°C Carrier gas: He Carrier gas flow rate: 30 mL / min Ionization method: EI Ion source temperature: 250°C Mass range: m / z = 30-1000

[0061] [2] Preparation of Glass Cloth Treatment Liquid [Examples 1-1 to 1-12, Comparative Examples 1-1 to 1-5] According to the blending ratios shown in Tables 1 and 2, the following components (A) and (B) were added dropwise to and mixed with 0.05% by mass acetic acid in water at 25°C to prepare glass cloth treatment liquids i to xvii. In Example 1-12, a mixed solvent of 0.05% by mass acetic acid in water and methanol was used. The obtained glass cloth treatment liquids were evaluated as follows. The results are shown in Tables 1 and 2.

[0062] [Stability of Glass Cloth Treatment Solution] The appearance of the obtained glass cloth treatment solution was visually inspected after leaving it to stand in an environment of 25°C for 1 day and 3 days, and evaluated according to the following criteria: ◯: Completely dissolved, forming a homogeneous aqueous solution; ×: Insoluble matter precipitated.

[0063]

[0064]

[0065] Each component shown in Tables 1 and 2 will be explained below. Component (A) KBM-503: 3-(methacryloyloxy)propyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) KBM-502: 3-(methacryloyloxy)propylmethyldimethoxysilane (Shin-Etsu Chemical Co., Ltd.) KBE-503: 3-(methacryloyloxy)propyltriethoxysilane (Shin-Etsu Chemical Co., Ltd.) Compound (1-3): organosilicon compound obtained in Synthesis Example 1 Component (B) Mixture (2): mixture of organosilicon compounds obtained in Synthesis Example 2 KBM-1063: 5-hexenyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) KBM-1083: 7-octenyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.)

[0066] [3] Production of Surface-Treated Glass Cloth [Examples 2-1 to 2-12, Comparative Examples 2-1 to 2-5] E-glass cloth (thickness: 95 μm, mass per unit area: 107 g / m) obtained by heating at 400° C. for 72 hours to remove the sizing agent was used. 2) was immersed in the glass cloth treatment liquid obtained in Examples 1-1 to 1-12 and Comparative Examples 1-1, 1-2, and 1-5, taken out, and then heated and dried at 110°C for 10 minutes to obtain a surface-treated glass cloth. In Comparative Examples 2-3 and 2-4, the stability of the glass cloth treatment liquid was low, and the glass cloth could not be surface-treated.

[0067] [4] Preparation of prepreg and cured prepreg The surface-treated glass cloth was impregnated with matrix resin (M-1), heated and dried at 100 ° C. for 10 minutes to remove the solvent, and a prepreg was obtained. Next, five prepregs were stacked and cured at 180 ° C. for 90 minutes using a vacuum press under a pressure of 2.5 MPa to produce a cured prepreg. Here, the matrix resin (M-1) was a mixture of 60 parts by mass of reactive low molecular weight polyphenylene ether (trade name: SA-9000, manufactured by SABIC Corporation), 25 parts by mass of liquid styrene butadiene rubber (trade name RICON 100, manufactured by Cray Valley Corporation), 15 parts by mass of triallyl isocyanurate, and 55 parts by mass of toluene (resin concentration 64.5% by mass), to which 2 parts of dicumyl peroxide were added as a curing catalyst.

[0068] The obtained cured prepreg was evaluated as follows. The results are shown in Tables 3 and 4. [Solder heat resistance test] The obtained cured prepreg was cut into a 5 cm square, boiled in ion-exchanged water for 2 hours, and then immersed in a solder bath at 260°C for 30 seconds. The appearance of the cured product was observed and rated according to the following criteria: Good: No blistering occurred. Bad: Blistering occurred. [Alkali immersion test] The obtained cured prepreg was cut into a 5 cm square, and the cut cured product was immersed in a 1 N aqueous sodium hydroxide solution for 24 hours. The appearance of the cured product was observed and rated according to the following criteria: Good: No whitening, or slight whitening at the edges. Fair: Whitening extended to near the center. Bad: Whitening occurred all over.

[0069]

[0070]

[0071] As shown in Table 1, the glass cloth treatment solutions i to xii obtained in Examples 1-1 to 1-12 had excellent storage stability. Furthermore, as shown in Table 3, the cured prepregs produced using glass cloth surface-treated with the glass cloth treatment solutions i to xii exhibited excellent solder heat resistance and alkali resistance. On the other hand, as shown in Table 4, the cured prepregs produced using glass cloth surface-treated with the glass cloth treatment solutions obtained in Comparative Examples 1-1 and 1-2 had poor alkali resistance. Furthermore, the glass cloth treatment solutions obtained in Comparative Examples 1-3 and 1-4 were poorly stable, making surface treatment of the glass cloth difficult. Furthermore, the cured prepreg produced using glass cloth surface-treated with the glass cloth treatment solution obtained in Comparative Example 1-5 had significantly poor solder heat resistance and alkali resistance.

Claims

1. A glass cloth treatment liquid in which (A) an organosilicon compound represented by the following formula (1) and (B) an organosilicon compound represented by the following formula (2) are dissolved in a solvent containing water, in which the concentration of component (A) is 0.05 to 2.0 mass %, and the concentration of component (B) is 0.05 to 2.0 mass %. (In the formula, R 1 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R 2 represents a hydrogen atom or a methyl group, Me represents a methyl group, X represents an oxygen atom or NH, R 3 represents a monovalent aliphatic unsaturated hydrocarbon group having 4 to 12 carbon atoms, m1 and m2 each independently represent an integer of 1 to 3, and n1 represents an integer of 1 to 12.

2. In the above formula (1), R 2 2. The glass cloth treatment liquid according to claim 1, wherein n is a methyl group and n1 is 3.

3. In the above formula (2), R 3 3. The glass cloth treatment liquid according to claim 1, wherein is a linear or branched alkenyl group having 4 to 8 carbon atoms.

4. The glass cloth treatment liquid according to any one of claims 1 to 3, wherein the water is adjusted to be acidic.

5. A surface-treated glass cloth, the surface of which has been treated with the glass cloth treatment liquid according to claim 4.

6. A prepreg comprising the surface-treated glass cloth according to claim 5 and a matrix resin impregnated into said surface-treated glass cloth.

7. A printed wiring board using the prepreg according to claim 6.

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