JP2000119406A - Frp molding composition and its product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an FRP molding composition and an FRP molded article excellent in resistance to alkalis. SOLUTION: An FRP molding composition contains urethane acrylate as a matrix resin and a glass fiber as a reinforcing material wherein the glass fiber is based on SiO2-Al2O3-MO and has a glass composition containing 1-10 mol% of ZnO, 5 mol% or less (including 0 mol%) of B2O3 and 0.5-5 mol% of TiO2 as the MO component. An FRP molded article contains urethane acrylate as a matrix resin and a glass fiber as a reinforcing material wherein the glass fiber contained at least in the surface of the article is based on SiO2- Al2O3-MO and has a glass composition containing 1-10 mol% of ZnO, 5 mol% or less (including 0 mol%) of B2O3 and 0.5-5 mol% of TiO2 as the MO component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an FRP molding composition and an FRP having excellent alkali resistance obtained by using the same.
Related to molded products.

[0002]

2. Description of the Related Art FRP (Fiber Reinforced Plastic)
Molded articles are used for various applications. In the composition used for the FRP molded article, generally, an unsaturated polyester resin is used as a matrix resin, and a glass fiber is used as a reinforcing fiber. Other types of reinforcing fibers include carbon fiber and aramid fiber, but glass fiber is widely used because of its excellent tensile strength, dimensional stability, electrical insulation, heat resistance, flexibility, and chemical resistance. I have. Among glass fibers, E glass containing almost no alkali metal is most frequently used because it is particularly excellent in weathering resistance and electrical insulation. In addition, C-glass is used for applications requiring strong acid resistance, and S-glass and cement products are used for applications requiring extremely high melting temperature, such as military and aerospace applications. Uses AR glass.

[0003]

By the way, recently, FR
Even in applications used in alkaline environments such as P concrete reinforcement, rock bolts, anchor bolts, FR
The use of P-shaped products is being considered. However, the conventional FRP molded products lack durability in an alkaline environment, and therefore, improvement is required.

Accordingly, an object of the present invention is to provide a composition for FRP molding and an FRP molded article having excellent alkali resistance.

[0005]

Means for Solving the Problems The present inventor has conducted various studies to solve the above-mentioned problems, and as a result of repeated experiments, it has been found that urethane acrylate must be used as a matrix resin, and that the It has been found that the ingredients need to be specifically selected. They have also found that it is necessary to use a composition close to E glass containing almost no alkali metal as the basic composition of glass fibers.

The basic composition of E glass is SiO_Two-Al_TwoO
_Three-CaO-B_TwoO_ThreeIt is. Alkaline water immersion resistance
From the standpoint of AR glass, AR glass with extremely excellent alkali resistance
Although AR glass can be used, AR glass has devitrification prevention and chemical resistance.
Al with excellent durability_TwoO_ThreeIs low, and
Na which is a lukari metal_TwoO and K_TwoUses a lot of O
Therefore, there is also a problem of lack of water resistance and elution of alkali components.
In that regard, E glass, which is a general-purpose glass fiber, is made of Al_TwoO_Three
And the use of alkali metals is suppressed.
It does not have any of the above problems of lath. However, E glass is B
_TwoO_ThreeIs contained in a large amount of 8 to 13 mol%,
Poor. Therefore, the present inventor has proposed that B _TwoO_ThreeComposition ratio of
In addition to selecting a composition with less
As a result, the MO composition added to improve spinnability
Generally, CaO or MgO is used as the component,
Almost never used ZnO is alkali resistant
Improving water immersion, TiO_TwoIf you mix
Completed the present invention, finding that lubricity is further improved
did.

Therefore, the composition for FRP molding according to the present invention contains urethane acrylate as a matrix resin, and the glass fiber as a reinforcing material is SiO ₂ —Al ₂
In the basic composition of the O ₃ -MO system, ZnO is contained in an amount of 1 to 10 mol% as the MO component, B ₂ O ₃ is contained in an amount of 5 mol% or less (including 0 mol%), and TiO ₂ is added in an amount of 0.1 mol%. The FRP molded product according to the present invention is characterized by having a glass composition containing 5 to 5 mol%, and further comprises a urethane acrylate as a matrix resin and a glass fiber as a reinforcing material. The glass fiber contained in the surface portion is SiO ₂ —Al ₂
O ₃ -MO system, wherein ZnO is 1 to
A glass composition containing 10 mol%, B ₂ O ₃ of 5 mol% or less (including 0 mol%), and TiO ₂ of 0.5 to 5 mol%.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, the urethane acrylate contained in the matrix resin is a compound having two or more (meth) acryloyl groups and two or more urethane bonds in one molecule, for example, having a hydroxyl group. (Meth) acrylate is linked with a polyvalent isocyanate, or a hydroxyl group-terminated oligoester or ether is linked with a (meth) acrylate having a hydroxyl group with a polyvalent isocyanate.

Examples of the (meth) acrylate having a hydroxyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and the like. Examples of the hydroxyl group-terminated oligoester and ether include propylene oxide adduct of phthalic acid, propylene oxide adduct of fumaric acid, propylene oxide adduct of bisphenol A, and ethylene oxide adduct of bisphenol A. Among these, a propylene oxide adduct of bisphenol A is particularly preferable from the viewpoint of the physical properties of a molded product obtained by curing. Examples of the polyvalent isocyanate compound include hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate (MDI), xylylene diisocyanate, tolylene diisocyanate, hydrogenated xylylene diisocyanate,
Hydrogenated diphenylmethane diisocyanate, naphthylene diisocyanate, paraphenylene diisocyanate,
Examples include dicyclohexylmethane diisocyanate, tetramethylene diisocyanate, those obtained by multiplying these polyisocyanate compounds, and adducts of these polyisocyanate compounds with polyhydric alcohols.

The matrix resin of the present invention may be composed only of urethane acrylate or may be composed of urethane acrylate and a polymerizable monomer. The type of the polymerizable monomer used as required is not limited as long as it is a vinyl monomer copolymerizable with urethane acrylate. For example, aromatic hydrocarbons such as styrene, methyl styrene, chlorostyrene, t-butyl styrene, and divinylbenzene; alkyl (meth) acrylates such as methyl methacrylate, methyl acrylate, ethyl methacrylate, and ethyl acrylate; Examples thereof include diallyl phthalate, and one or more of these can be used as appropriate. Among them, styrene is particularly preferred in view of the physical properties of a molded product obtained by curing. The amount of the polymerizable monomer used is 2 in the matrix resin.
It is preferably from 0 to 70% by weight, particularly preferably from 30 to 50% by weight.

In the matrix resin of the present invention, other polymers may be used in addition to the essential urethane acrylate. Examples of the polymer used in combination here include unsaturated polyester and epoxy acrylate. Glass fibers used in the composition for FRP molding of the present invention,
Basic composition is SiO ₂ -Al ₂ O ₃ -MO-based. The mixing ratio of these is not particularly limited, but the SiO ₂ content in the whole glass composition is 45 to 70 mol%,
_The content of ₂ O ₃ is 5 to 20 mol% and the content of MO is 1
It is preferably from 0 to 35 mol%. And the M
1 to 10 mol% of ZnO as an O component, and B ₂
It is necessary that the content of O ₃ be 5 mol% or less (including 0 mol%) and the content of TiO ₂ should be 0.5 to 5 mol%. Other MO components include CaO, MgO, BaO,
MnO, may include SnO, FeO, and _{Fe 2 O 3, P 2 O} 5. The upper limit of the ZnO content is required to be 10 mol% from the viewpoint of spinnability. Also, T
It is also necessary that the upper limit of the content of iO ₂ is 5 mol% from the viewpoint of spinnability. As such a glass fiber, a commercial product RS220RL-51 manufactured by Nitto Boseki Co., Ltd. is available.
0 and so on.

The form of the glass fiber is variously selected depending on the molding method. For example, a roving in which strands are aligned, a roving cloth in which the strands are woven, a chopped strand in which only a strand is cut, a chopped strand in which a strand is formed There are mats, yarns obtained by twisting strands, glass cloth obtained by weaving the yarns, and milled fibers obtained by simply grinding the strands.

The proportion of the glass fiber used in the matrix resin varies depending on the molding method, and is basically the same as usual. However, for example, when the glass fiber is used in the form of a roving for drawing, etc. Is 40-90%, 2% when used for hand lay-up etc. in the form of a mat
0 to 40%. In the FRP molding composition of the present invention, as usual, a curing agent, a release agent, a thickener,
A coloring agent and the like can be included as needed.

The molded article according to the present invention can be obtained by molding using this FRP molding composition alone or in combination with a general FRP molding composition containing general-purpose glass fibers. In the latter case, It is necessary that at least the surface part of the molded article is the composition of the present invention. In this case, it is necessary that the composition of the present invention is contained in the surface portion in the molded article at a thickness of at least 1 mm or more from the surface, and preferably at least 2 mm. When the thickness of the composition of the present invention from the surface of the molded article is less than 1 mm, the alkali resistance and gloss of the molded article are reduced. The molding method is not particularly limited, but examples of the molding method include a hand lay-up method, a spray-up method, a resin injection method, a drawing method, and a gel coating is performed as necessary.

The FRP molding composition according to the present invention comprises S
It can be used for MC and BMC.

[0016]

Examples-Examples-100 parts by weight of hydroxyethyl methacrylate and a propylene oxide adduct of bisphenol A having a hydroxyl value of 318 (trade name: Bisol 2PN, manufactured by Toho Chemical Industry) 1
27 parts by weight, polyfunctional diphenylmethane diisocyanate having an NCO content of 31.8% (trade name: Sumidur 44)
V-10, manufactured by Sumitomo Bayer Urethane) 51 parts by weight to 60
The mixture was added dropwise at 2 ° C. over 2 hours, and then reacted at the same temperature for 2 hours. Further, 100 parts by weight of a urethane acrylate resin obtained by mixing a compound obtained by raising the temperature to 100 ° C. and reacting for 2 hours with a styrene monomer as a polymerizable monomer to a concentration of 35% by weight was mixed with perbutyl O as a curing agent.
1.5% by weight (manufactured by Nippon Oil & Fat), Mo as an internal release agent
ldo Width INT 1850 (Axel)
After adding 0.7% by weight, using a glass roving having the composition shown in Table 2, it was formed into a rod having a diameter of 5 mm by a drawing method under the following conditions, and cut into 300 mm lengths.
For 2 hours to obtain an FRP rod.

Molding conditions : Pultrex PUL molding machine
Using TREX, using a mold having a diameter of 5 mm and a length of 80 cm, an inlet temperature of 80 to 100 ° C. and an intermediate temperature of 100 to 120.
C.-The outlet temperature was set at 120 to 140.degree. C., and the molding speed was set at 30 cm / min. This FRP rod (test piece) was subjected to an alkaline water immersion test under the following conditions, and then to a strength measurement under the following conditions. The results are as shown in Table 1.

Alkali-resistant water immersion test : A container containing mixed alkaline water containing 0.2% by weight of calcium hydroxide, 1.0% by weight of sodium hydroxide, and 1.4% by weight of potassium hydroxide was placed in a thermostat. The specimen was left at 60 ° C., and the test piece was immersed therein for one month, two months, and three months. Tensile strength test : Autograph AG25TD manufactured by Shimadzu Corporation
Was used as a measuring machine at a distance between chucks of 160 mm and a crosshead speed of 5 mm / min.

Comparative Example 1 An FRP rod was prepared and evaluated in the same manner as in Example except that the glass was changed to E glass. The results are as shown in Table 1. The glass composition of E glass is as shown in Table 2. -Comparative Example 2-An FRP rod was produced and evaluated in the same manner as in the example except that the glass was changed to T glass. The results are as shown in Table 1. Table 2 shows the glass composition of the T glass.

Comparative Example 3 1.0 mol of methacrylic acid was added to 1 mol of epoxy groups of a bisphenol A epoxy resin having an epoxy equivalent of 365.
25 mol was added dropwise at 105 ° C. over 2 hours, then the temperature was raised to 110 ° C. and reacted for 5 hours, and the vinyl ester resin (styrene content 44%) obtained was shaken to 100 parts by weight. 2.0% by weight of Perbutyl O (manufactured by NOF Corporation) as a curing agent, 0.5% by weight of Parkadox 16 (manufactured by Kayaku Akzo), and Mold as an internal release agent
o Width INT 1850 (Axel) 0.7
A FRP rod was prepared and evaluated in the same manner as in the example except that the weight% was added. The results are as shown in Table 1.

Comparative Example 4 An FRP rod was prepared and evaluated in the same manner as in Comparative Example 3 except that the glass was changed to F glass. The results are as shown in Table 1. Comparative Example 5 An FRP rod was prepared and evaluated in the same manner as in Comparative Example 3 except that the glass was changed to T glass. The results are as shown in Table 1.

[0022]

[Table 1]

[0023]

[Table 2]

Table 1 shows that when the urethane acrylate resin is used as the matrix resin and the glass of the composition of the present invention is used as the glass fiber, both the initial strength and the strength retention after immersion are high.

[0025]

The composition for FRP molding according to the present invention comprises:
Since the matrix resin and glass fiber are particularly selected, it is possible to obtain an FRP molded product having excellent alkali resistance. Since the FRP molded article according to the present invention can be obtained in a state having the above composition on at least the surface portion of the molded article,
There is no alkali elution and excellent alkali resistance.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Ken Morita 5-8 Nishiburi-cho, Suita-shi, Osaka F-term (reference) in Nippon Shokubai Co., Ltd. 4F072 AA02 AA07 AB09 AD43 AL01 AL17 4G062 AA05 AA15 BB01 CC10 DA05 DA06 DB03 DB04 DC01 DC02 DC03 DD01 DE03 DF01 EA01 EA10 EB01 EC01 ED01 EE01 EF01 EG01 FA01 FB02 FB03 FC01 FD01 FE01 FF01 FG01 FH01 FJ01 FK01 FL01 GA01 GB01 GC01 GD01 GE01 HH01 HH03 HHH HH HH HH HH HH HH HH HH HH H KK07 KK10 MM15 NN33 PP14

Claims (4)

[Claims] An FRP molding composition containing urethane acrylate as a matrix resin and glass fiber as a reinforcing material, wherein the glass fiber is SiO ₂ —Al ₂ O ₃
A MO system, wherein ZnO is 1 to 10 as the MO component;
Wherein mol%, and the B ₂ O ₃ 5 mole% or less (0 mol%
And TiO _{2 in an amount} of 0.5 to 5 mol%
A composition for FRP molding, comprising a glass composition containing: 2. The glass composition wherein the SiO ₂ content is 45 to 70.
_2. The FRP molding composition according to claim 1, wherein the FRP composition has an Al ₂ O ₃ content of 5 to 20 mol% and an MO content of 10 to 35 mol%. 3. An FRP molded product containing urethane acrylate as a matrix resin and glass fiber as a reinforcing material, wherein at least the glass fiber contained in the surface of the molded product is a SiO ₂ —Al ₂ O ₃ —MO system. And the MO
1 to 10 mol% of ZnO as a component, and B ₂ O
₃ is 5 mol% or less (including 0 mol%),
Characterized in that it is a glass composition comprising TiO ₂ 0.5 to 5 mol%, FRP molded articles. 4. The glass fiber contained in the surface portion of the molded article has a SiO ₂ content of 45 to 70 mol%.
l ₂ O ₃ content is 5 to 20 mol%, MO content of 10 to 35 mol%, FRP molded article according to claim 3.