JPH0312346A - Surface treating agent for glass fiber - Google Patents

Abstract

PURPOSE:To obtain a surface treating agent for glass fibers for glass fiber reinforced plastics having high adhesive property to resin and superior heat resistance at the time of soldering by using specified water soluble azidosilane and a silane coupling agent having a double bond as bases. CONSTITUTION:Azidosilane represented by the formula [where R1 is hydroxy, alkoxy, aryloxy or organo-oxycarbonyl, R2 is alkyl, cycloalkyl, aryl, alkaryl or aralkyl, R is an org. group, R3 is -OCOCR'N2, -OCON3 or -SO2N3, R' is H, alkyl, cycloalkyl or aryl, 1<=x<=3, 0<=y<=2 and 1<=(x+y)<=3], e.g. 3-(trimethoxysilyl)propyldiazo acetate and a silane coupling agent having a double bond in the molecule, e.g. N-beta-(N-vinylbenzylaminoethyl)-gamma- aminopropyltrimethoxysilane are used as bases to obtain a surface treating agent for glass fibers.

Description

[Detailed description of the invention] [Industrial application field] Mizumoto improves the adhesion between glass fiber base materials and plastics such as thermosetting resins or thermoplastic resins, and improves the heat resistance of these composite plastics. This invention relates to a silane coupling agent used as a surface treatment agent for glass fibers.

[Prior Art] Composite materials made by treating glass fiber sheets such as woven fabrics, non-woven fabrics, and paper made of glass fibers with matrix materials such as epoxy resins, phenolic resins, polyimide resins, and polyamide resins have already been widely used. These are well known and widely used for various purposes.

However, among these composite materials, laminates for printed wiring boards using epoxy resin or polyimide resin as a matrix resin have recently shown remarkable growth. However, since this 8!1 layer board for printed wiring boards is immersed in molten solder during the wiring process, it is required to have strong heat resistance.

It is also known that the adhesion of the matrix resin coating for imparting strong heat resistance can be enhanced by using an azidosilane coupling agent. (
See, eg, US Pat. No. 3,585,103).

However, since such coupling agents are expensive,
There was a need for an improved method that would reduce the amount of azidosilane coupling agent without affecting the adhesion of the resin to the glass fiber sheet. Therefore, a method was proposed to reduce the amount of the coupling agent without reducing the adhesion of the resin to the silicon material by substituting the coupling agent with a cheaper organosilicon compound (Japanese Patent Application Laid-Open No. 59-168034).

[Problem to be solved by the invention] The bond between glass fiber and matrix resin can be made stronger by bridging the interface between inorganic and organic materials by modifying the surface of glass fiber with a silane coupling agent. Therefore, only the silane coupling agent bonded to the glass fiber surface acts effectively to improve adhesion.

However, in the method described in JP-A No. 59-168034, since a relatively large amount of silane coupling agent is added to the mixture, a large amount of coupling agent is wasted, and it is difficult to obtain sufficient adhesion improvement. In addition to aggravating the problem, adding the sizing agent to the sizing agent during spinning of high-temperature glass fibers and directly applying it to the surface of the glass fibers had a fire prevention effect.

[Means for Solving the Problems] The present invention involves adhering together an azide silane that is soluble in water and a silane coupling agent having a double bond in the molecule to a glass fiber base material for a printed wiring board. As a result, we have succeeded in solving the problems in the conventional method and obtaining a surface treatment agent for glass fibers for glass fiber reinforced plastics that has improved adhesion to resin and excellent solder heat resistance.

That is, the present invention is based on the general formula [wherein R1 is a group selected from the group consisting of hydroxy, alkoxy, aryloxy, organooxycarbonyl, and azido group, and R2 is alkyl, cycloalkyl,
A group selected from the group consisting of aryl, alkaryl, and aral group, R is a l1lJ group, and R3 is (wherein R' is hydrogen, alkyl, cycloalkyl, aryl and where RIT is a group selected from the group consisting of alkyl, cycloalkyl and aryl bases; and x and y are 1≦X ≦3.
A glass fiber surface treatment agent characterized in that the main ingredients are an azide silane represented by C, which is an integer of 0≦y≦2.1≦X+y≦3, and a silane coupling agent having a double bond in the molecule. This is a summary.

Preferably, the organic group 1 in the formula (1) of the azidosilane in the glass fiber surface treatment agent of the present invention is a divalent hydrocarbon group, a halogen-substituted hydrocarbon group, a hydrocarbon-oxy-hydrocarbon group, a hydrocarbon group, etc. -thio-hydrocarbon group and hydrocarbon-sulfonyl-hydrocarbon group.

In a most preferred embodiment of the invention R is an alkylene group such as a linear and molecular C-C2o alkylene group (e.g. methylene, 1-tylene, trimethylene,
tetramethylene, pentamethylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, octadecamethylene groups, etc.); cycloalkylene groups such as 03-C2o cycloalkylene groups (e.g. cyclohexylene, cyclopentane, cycloalkylene, cyclobutylene groups); etc.); arylene groups (e.g. 〇-m- and p-
phenylene, naphthylene, biphenylene groups, etc.); arylene-dialkylene groups (e.g. 〇-1m- and p-
- lxylylene diethylene 0-lm- and p-phenylene diethylene groups, etc.); alkylene-diarylene 1
iS [e.g. methylenebis(0-1m- and p-phenylene), ethylenebis(0-1m- and p-phenylene) groups, etc.]; cycloalkylene-dialkylene groups (
(e.g. 1,2- and 1,3- and 1,4-cyclohexane-dimethylene, 1,2- and 1,3-cyclopentane-dimethylene groups); and alkylene-oxy-
alkylene group, arylene-oxy-arylene group, alkalylene-oxy-arylene group, alkylene-oxy-arylene group, aralkylene-oxy-
alkylene groups, aralkylene-oxy-aralkylene groups, etc., and the corresponding thio and sulfonyl groups (e.g. ethylene-oxy-ethylene, propylene-oxy-
Butylene, phenylene-oxy-phenylene, methylenephenylene-oxy-phenylenemethylene, phenylenemethylene-oxy-methylenephenylene, ethylene-thio-ethylene, phenylene-thio-phenylene, phenylenemethylene-thio-methylenephenylene, butylene-
(sulfonyl-butylene group, etc.); a divalent organic group selected from the group consisting of; It is understood by those skilled in the art that R can be any other functional group that is substantially inert to reactions using these compounds (e.g., esters, sulfonic esters, amides, sulfonamides, etc.). It will be clear that the urethanes may also be included (such as urethanes) as described in Thomson US Pat. No. 3,697.551.

Preferably, 1 or ' is a hydrogen, alkyl, cycloalkyl, aryl or 1000 R'' group.

The most preferred alkyl, cycloalkyl and aryl groups are methyl, ethyl, propyl, butyl, isobutyl, cyclohexyl, cyclohebutyl, phenyl, tolyl, and the like. The group Rrr may be alkyl, cycloalkyl or aryl, the most preferred groups being methyl, ethyl, propyl, butyl, isobutyl, cyclohexyl, cycloheptyl, phenyl, tolyl and the like. Generally R1 is hydroxy or a hydrolyzable group. Typical hydrolysable groups include alkoxy groups, including linear and branched C-C2o alkoxy groups (e.g., methoxy, ethoxy, propoxy, butoxy, isobutoxy, octadecyloxy, etc.); aryloxy groups ( For example, phenoxy): Aliphatic oxycarbonyl!
organoxycarbonylalkyl rules, including alicyclic oxycarbonyl groups (e.g., cyclohexylcarbonyloxy, etc.), aromatic oxycarbonyl groups (e.g., benzoyloxy, xylyloxy, etc.); selected from the group consisting of aralkyl groups (eg methyl, ethyl, propyl, isopropyl, butyl, hexyl, cyclohexyl, cyclohebutyl, phenyl, tolyl, benzyl, xylyl, etc.);

Typical azidosilane coupling agents are $-(trimethoxysilyl)propyl diazoacetate 2-(methyldichlorosilyl)ethyl diazoacetate p-(trimethoxysilyl)benzyl diazoabamoyl 1decyl diazoacetate 4-(trimethoxysilyl)butyl α- Diazoprogonate 3-(ethyldimethoxysilyl)propyl α-diazo-
α-Phenylacetate 2-(trimethoxysilyl)ethyl α-diazoα-carbophenoxyacetate 3-(trimethoxysilyl)propyl azidoformate 3-(methyldimethoxysilyl)propyl azidoformate 2-chloro- 3-[3-(trimethoxysilyl)propoxyconityl azidoformate 3-(triacytosilyl)propyl azidoformate 2-(trimethoxysilyl)ethyl azidoformate 3-(triacetoxysilyl)propyl azidoformate 2- 3-(trimethoxysilyl)propoxyconityl azidoformate 3-(methyldiacetosilyl)propyl azidoformate 2-(ethyldibrobionyloxysilyl)ethyl azidoformate p-(trimethoxysilyl)phenyl azidoformate 4-(Jetoxychlorosilyl)butyl azidoformate 4-(ethyldimethoxysilyl)cyclohexylazidoformate 3-(phenyldichlorosilyl)propyl azidoformate 4-(trisdimethylaminosilyl)butyl azidoformate 5 (trimethoxysilyl)amylsulfonyl azide 4-(trimethoxysilyl)cyclohexylsulfonyl azide 3-chloro0-6- (trimethoxysilyl)hexylsulfonyl azide 6-(trimethoxysilyl)hexylsulfonyl azide 3-( dimethylaminodimethylsilyl)propylsulfonyl azide 2-(triethoxysilyl)ethylsulfonyl azide 3-(methyldimethoxysilyl)-propylsulfonyl azide 3-(trimethoxysilyl)propylsulfonyl azide 4-[jethoxy-(4-sulfonylazidobutyl) ) Silyl 1-butylsulfonyl azide p-(trimethoxysilyl)benzenesulfonyl azide 2-(trimethoxysilyl)ethylbenzenesulfonyl azide N-3-(triethoxysilyl)propyl-N'-3-
Azidosulfonylpropylurea N-3-<triethoxysilyl)propyl-N'-m-azidosulfonylphenylurea.

Many of the azidosilane compounds used in the present invention have 20 to 2
At 5°C and atmospheric pressure, it is liquid, but some of it is solid.

The silane coupling agent having a double bond in the molecule used in the present invention can be used without particular restrictions.

Representative examples include γ-methacryloxypropyltrimethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, vinyltriacetoxysilane, and vinyltrimethoxysilane. I can do it.

The concentration of the surface treatment agent solution, which is mainly composed of azidosilane and a silane coupling agent having a double bond in the molecule, is usually 0.
2 to 3.0% by weight, preferably 0.5 to 1.5% by weight, pick-up to the glass fiber substrate is usually 30%, and the amount attached to the glass fiber is usually 0.06 to 0. .50'
Use it so that it becomes ff1ffi%.

These surface treatment agents are 1. Although it is mainly used as an aqueous solution, it can also be used as a mixed solution of an organic solvent such as alcohol and water.

The surface treatment agent of the present invention comprising the above-mentioned components can be applied to glass fibers according to a conventional method.

For example, it can be applied with a size applicator to the glass fiber filaments that are being spun from the bushing, or it can be impregnated or applied to molded products such as silk, nonwovens, mats, paper, etc. and dried, a so-called secondary coat. It can also be applied as

The glass fiber base material can be anything from filaments being spun as mentioned above to fibrous materials such as yarn, strands, chopped strands, and sheet materials such as woven fabrics, non-woven fabrics, mats, and paper. It can be processed without any problem.

[Function] However, in order to increase the adhesion with the resin and improve the heat resistance of the composite plastic, when forming the composite plastic using the glass fiber base material treated with the surface treatment agent of the present invention, it is necessary to In order to initiate a bonding reaction by the azide group of the ring material, it is important to decompose the azide group by heating at a sufficient temperature and time. The temperature suitable for decomposition can vary widely depending on the type of azidosilane used, but is generally about 70 to about 350°C, preferably about 1
The temperature ranges from 20 to about 250°C. The heating time varies depending on the type of silane coupling agent having a double bond, but is preferably about 12 to about 10 minutes.

Radicals are generated by the reaction -N3→-N:. This radical acts on the double bond of the silane coupling agent which has a double bond in the other molecule, causing a polymerization reaction. Therefore, when a thermosetting resin or a thermoplastic resin such as an epoxy resin or a polyester resin is coated, impregnated, or mixed on the glass fiber H substrate to which the surface treatment agent of the present invention has been applied, and then heated and pressed, it is subjected to the action of the radicals. The silane coupling agent 1, which has a double bond in its molecule, causes a polymerization reaction or a crosslinking reaction, and the functional group of the silane coupling agent reacts with the resin. There is “entanglement” caused by cross-linking rather than physical objects.
An interfacial layer is formed that forms a stronger bond to the resin, resulting in enhanced adhesion with the matrix resin, thereby significantly improving the solder heat resistance of the composite plastic.

[Examples] The following examples are intended to explain the present invention in more detail, but are not intended to limit the present invention. All percentages are by weight unless otherwise specified. Furthermore, the heat resistance was measured using the following method.

Solder heat resistance test: After boiling a laminate test piece in a pressure cooker at 133°C, immerse it in a 280°C solder bath for 20 seconds, and after taking it out, examine the surface of the test piece for flaking or peeling to determine the occurrence of these defects. The boiling time was defined as the solder heat resistance time.

Example 1 1) Glass cloth WEA-18W (manufactured by Nittobo) Glass fiber fabric deoiled by heat cleaning 2) Treatment liquid Azidosilane [AZ-CUP MC (manufactured by Percules)] 00.1% N-β-N-
(vinylbenzylaminoethyl) γ-aminopropyltrimethoxysilane hydrochloride [5Z6032 (manufactured by Toshi Silicone)] 1.0% acetic acid 1.0% 3) Surface treatment The glass cloth of 1) was mixed with the treatment solution of 2) (pH becomes 4)
Soak in and squeeze to 30% with a squeeze roll. This is dried for 5 minutes in a dryer at a temperature of 110°C.

4) Creation of laminate Epoxy resin varnish Epoxy resin (Epicoat 1°01 manufactured by Shell Chemical Co., Ltd.)
100 heavy stones part dicyandiamide
2 parts by weight benzyldimethylamine 0.
2 parts ffi Methyl oxytol Approximately 1 oota part A surface-treated glass cloth was immersed in the epoxy resin varnish having the above composition, air-dried, and then dried at 140°C for 10 minutes to obtain 141.2 parts by weight of resin ff and 58 parts by weight of glass cloth.
．． A prepreg consisting of 1 part of 81ff was obtained.

8 sheets of this prepreg were stacked, 35μIll thick copper foil was stacked on both sides, and heated at 170℃, 40K9/Cr112.
Compression molding was performed for 70 minutes to obtain a printed wiring board made of a copper clad laminate. Furthermore, after removing the copper foil by etching the entire surface, washing with water and air drying, 5011Ill x 50
A test piece with a size of m was prepared. Next, the solder heat resistance time of the obtained laminate was measured.

The results are shown in Table 1.

Example 2 A silane coupling agent having a double bond in the molecule is
Methacryloxypropyltrimethoxysilane [5H60
30 (manufactured by Toshi Silicone)], the same experiment as in Example 1 was repeated to prepare a test piece, and the solder heat resistance time was measured. The results are shown in Table 1.

Example 3 Glass cloth was made of WEA-18 with a mass of 215 g/TrL2
W was replaced with WEA-116E (Nittobo W!J) with a mass of 105 g/TrL2, and azidosilane [AZ-CUP
MC] was 0.05%, and the silane coupling agent having a single bond in the molecule was vinyltriacetoxysilane [5
The experiment of Example 1 was repeated except that H6075 (manufactured by Toshi Silicone) was changed to 10.5%, and therefore the amount of water was changed to 98.45%. Table 1 shows the solder heat resistance time.

Example 4 Example except that the silane coupling agent having a double bond in the molecule was changed to vinyltrimethoxysilane [SZ 6300 (manufactured by Toshi Silicone) 10.8%, and therefore the water was changed to 98.15%. The same experiment as in 3 was conducted, and the obtained solder heat resistance times are shown in Table 1.

Comparative Examples 1 to 2 An experiment was conducted by repeating the procedure of Example 1 except that azidosilane was removed from the formulation of Example 1 (Comparative Example 1), and in the same manner, azidosilane was removed from the formulation of Example 3 and Example 3 We conducted the same experiment as (Comparative Example 2) and measured the heat resistance time of each solder.The results are shown in Table 1.In addition, this surface treatment agent for glass fibers has both good water solubility and storage stability as an aqueous solution. In addition, since there is no risk of deterioration of the working environment or ignition during use, it has a wide range of applications in the field of composite plastics that require heat resistance, including printed wiring boards.

Claims (1)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) [In the formula, R_1 is hydroxy, alkoxy, aryloxy,
R_2 is a group selected from the group consisting of organooxycarbonyl and azide groups, R_2 is a group selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl and aral groups, R is an organic group, R_3 There are ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. a group selected from the group consisting of alkyl, cycloalkyl and aryl groups), and x and y are 1≦x≦3, 0≦
A surface treatment agent for glass fibers, characterized in that the main ingredients are an azide silane represented by y≦2, an integer consisting of 1≦x+y≦3 and a silane coupling agent having a double bond in the molecule.