JP5548317B2 - Molding materials and molded products - Google Patents

Description

The present invention relates to a radically polymerizable resin composition containing a (meth) acryloyl group-containing polyurethane which can be molded under various conditions from a molding temperature of room temperature to a high temperature and a molding method of filament winding, lamination, RTM, vacuum infusion and press. Articles, molding materials and molded articles.

As fiber reinforced plastics (FRP), for example, those containing thermosetting resins such as unsaturated polyester resins, vinyl ester resins, epoxy resins, phenol resins, and glass fibers as fiber reinforcing materials are known.
In particular, FRP containing unsaturated polyester resin or vinyl ester resin and glass fiber can adjust the viscosity of the molding material by using a polymerizable unsaturated monomer such as styrene in combination with low to high temperature. It can be cured in a wide temperature range up to, so it is used in the widest range.

On the other hand, in the fields of aerospace, sports, automobiles, pressure pipes, pressure vessels, windmills, etc., there is a demand for the development of materials that achieve both high strength and light weight. Various studies are underway to achieve both weight reduction.
As FRP capable of achieving both high strength and light weight, for example, carbon fiber reinforced plastic using carbon fiber instead of conventional glass fiber is known. Carbon fiber is a fiber with a fine graphite crystal structure that is made by converting polyacrylonitrile resin, organic matter such as pitch from petroleum and coal into fibers, and then undergoing a special heat treatment process. It is lighter and has a feature of high strength.
Therefore, FRP obtained by using carbon fiber and epoxy resin has much superior strength compared with conventional glass fiber, and further, has achieved a weight reduction of about 25% or more of conventional products. It was a thing.

However, since FRP containing unsaturated polyester resin or vinyl ester resin and glass fiber or carbon fiber has insufficient toughness of the resin itself, even when used as FRP, mechanical strength, fatigue characteristics, etc. The characteristics may be insufficient. For this reason, in particular, development to applications having high strength such as pressure pipes, pressure vessels, windmill blades, vehicle structural members, civil engineering-related structural members, and the like has been limited. That is, the characteristic that the mechanical strength is insufficient is due to the so-called brittle characteristic of the resin itself, and an attempt to improve the elongation characteristic of the resin itself can be considered in order to improve the brittleness. However, in the conventional method, as the elongation is improved, the heat resistance and the heat distortion temperature are remarkably lowered, and it is difficult to maintain both the elongation and the heat resistance.
On the other hand, in order to improve the mechanical strength, use of an epoxy resin having high toughness has been studied. However, the epoxy resin generally has a high viscosity, and it is difficult to adjust the viscosity by using a polymerizable unsaturated monomer such as an unsaturated polyester or vinyl ester. There were many restrictions. In addition, epoxy resins are usually difficult to cure at room temperature and require a long time for curing, which is a major problem in improving production efficiency.
Accordingly, there has been a strong demand for the development of a resin that is excellent in viscosity adjustment and molding curability while improving the elongation rate of the resin itself and maintaining heat resistance.

As FRP containing vinyl ester resin, unsaturated polyester resin, and carbon fiber, for example, a composition comprising a specific epoxy group-containing vinyl ester, a radical polymerizable monomer, a curing agent, and carbon fiber is cured. A carbon fiber reinforced resin composite material obtained in this manner is known (for example, see Patent Document 1).
Moreover, as FRP containing vinyl ester resin and carbon fiber, for example, vinyl ester resin consisting of vinyl ester and styrene monomer, or vinyl ester resin consisting of methacryl monomer and photopolymerization initiator, glass A carbon fiber reinforced resin composite material obtained by obtaining a molded product by filament winding while impregnating fibers or carbon fibers, and then curing the molded product with light generated by a fluorescent lamp and a redox reaction is known. (For example, refer to Patent Document 2).

However, the carbon fiber reinforced resin composite material described in Patent Document 1 may also have insufficient adhesion between the resin and the carbon fiber, and as a result, it is difficult to use for manufacturing a high-strength molded product. There was a case.
The carbon fiber reinforced resin composite material described in Patent Document 2 is also difficult to impart a level of strength comparable to that of conventional epoxy resin-based molding materials, and is therefore used for the production of high-strength molded products. It was still difficult to do.

International Publication No. 2004/067612 JP 2004-034661 A

The problem to be solved by the present invention includes a (meth) acryloyl group-containing polyurethane having a low viscosity and excellent curability capable of producing a molded product having both mechanical strength and heat resistance while improving elongation. It is to provide a radical polymerizable resin composition, a molding material and a molded article.

The present invention provides a (meth) acryloyl group-containing polyurethane (A) having a structure represented by the following general formula (I) and a (meth) acryloyl group-containing polyurethane (B) having a structure represented by the following general formula (II): And a molding material obtained by using a radical polymerizable resin composition containing a radical polymerizable unsaturated monomer (C) , a fiber reinforcing material (D), and an organic peroxide (E) It is.

（一般式（Ｉ）中のＹは、脂肪族環式構造含有アルキレン基を表し、Ｔは、脂肪族環式構造含有アルキレン基又は鎖状アルキレン基を表し、Ｘは、（メタ）アクリロイル基を含む原子団を表す。）

(Y in general formula (I) represents an aliphatic cyclic structure-containing alkylene group, T represents an aliphatic cyclic structure-containing alkylene group or a chain alkylene group, and X represents a (meth) acryloyl group. (Indicates the atomic group that contains it.)

（一般式（ＩＩ）中のＹ´は、炭素原子数２以上であるオキシアルキレン単位を有するポリエーテル骨格を有する構造を表し、Ｔ´は、芳香族構造含有化合物、脂肪族環式構造含有アルキレン基又は鎖状アルキレン基を表し、Ｘは、（メタ）アクリロイル基を含む原子団を表す。）

(Y ′ in the general formula (II) represents a structure having a polyether skeleton having an oxyalkylene unit having 2 or more carbon atoms, and T ′ represents an aromatic structure-containing compound or an aliphatic cyclic structure-containing alkylene. Represents a group or a chain alkylene group, and X represents an atomic group containing a (meth) acryloyl group.

According to the present invention, a radically polymerizable resin composition containing a (meth) acryloyl group-containing polyurethane having low viscosity and excellent curability capable of producing a molded article having excellent elongation, mechanical strength and heat resistance. A molding material and a molded product can be provided.

2 is an IR spectrum diagram of polyurethane (I) obtained in Synthesis Example 1. FIG.

The best mode of the radical polymerizable resin composition of the present invention will be described.

The radical polymerizable resin composition of the present invention has a (meth) acryloyl group-containing polyurethane (A) having a structure represented by the following general formula (I) and a structure represented by the following general formula (II) (meth) It contains an acryloyl group-containing polyurethane (B) and a radically polymerizable unsaturated monomer (C).

The (meth) acryloyl group-containing polyurethane (A) used in the present invention has a structure represented by the following general formula (I).

（一般式（Ｉ）中のＹは、脂肪族環式構造含有アルキレン基を表し、Ｔは、脂肪族環式構造含有アルキレン基又は鎖状アルキレン基を表し、Ｘは、（メタ）アクリロイル基を含む原子団を表す。）

(Y in general formula (I) represents an aliphatic cyclic structure-containing alkylene group, T represents an aliphatic cyclic structure-containing alkylene group or a chain alkylene group, and X represents a (meth) acryloyl group. (Indicates the atomic group that contains it.)

Y in the general formula (I) is an aliphatic cyclic structure-containing alkylene group as described above, and is composed of an aliphatic cyclic structure and a chain aliphatic alkylene structure.
Here, when the alkylene group does not have an aliphatic cyclic structure and is a linear or branched aliphatic structure or an aromatic ring structure, it is difficult to achieve both excellent heat resistance and elongation rate, and thus easily causes deformation and the like. There is a case.

The molecular weight of the aliphatic cyclic structure-containing alkylene group is preferably relatively small, and more preferably 65 to 270. Specifically, the aliphatic cyclic structure-containing alkylene group includes an aliphatic cyclic structure-containing polyol (a1) described later and an aliphatic cyclic structure-containing alkylene group or a chain alkylene group-containing polyisocyanate (a2) described later. ) And a structure derived from (a1) introduced into the formula (I) by reacting with (), the molecular weight of which corresponds to the molecular weight obtained by removing two hydroxyl groups from (a1) described later.
For example, when the aliphatic cyclic structure-containing polyol (a1) has a molecular weight in the range of 100 to 300, the aliphatic cyclic structure-containing alkylene group has a molecular weight in the range of 100 to 300 and 2 This is the difference from the formula weight 34 of the two hydroxyl groups.
The molecular weight is a value calculated based on the formula weight of the element constituting the aliphatic cyclic structure-containing alkylene group.

T in the general formula (I) is an aliphatic cyclic structure-containing alkylene group or a chain alkylene group, specifically, an aliphatic cyclic structure-containing alkylene group or a chain alkylene group-containing polyisocyanate described later. The structure derived from (a2) is mentioned.
Even if Y in the general formula (I) is an aliphatic cyclic structure-containing alkylene group, the T is not an aliphatic cyclic structure-containing alkylene group or a chain alkylene group, but has an aromatic ring structure, for example. In the case of a hydrocarbon group, there are cases where excellent elongation, mechanical strength, and heat resistance cannot be combined.

X in the general formula (I) is an atomic group containing a (meth) acryloyl group. Specifically, a structure derived from an active hydrogen atom-containing (meth) acrylate (a3) described later is mentioned, and the structure is (meth) in the molecule of the (meth) acryloyl group-containing polyurethane (A) used in the present invention. Adds an acryloyl group.
The number of the (meth) acryloyl groups is preferably 1 to 10 and more preferably 1 to 3 at the molecular ends of the (meth) acryloyl group-containing polyurethane (A).

As said (meth) acryloyl group containing polyurethane (A), it is preferable to use the thing of molecular weight 500-1500, and it is more preferable to use the thing of molecular weight 500-1200.
In addition, the said molecular weight points out the value calculated | required from the total amount based on the formula amount of the atom which comprises a (meth) acryloyl group containing polyurethane (A).

The (meth) acryloyl group-containing polyurethane (A) includes, for example, an aliphatic cyclic structure-containing polyol (a1), an aliphatic cyclic structure-containing alkylene group or a chain alkylene group-containing polyisocyanate (a2), and active hydrogen. It can manufacture using an atom containing (meth) acrylate (a3).
More specifically, for example, by reacting an aliphatic cyclic structure-containing polyol (a1) with an aliphatic cyclic structure-containing alkylene group or a chain alkylene group-containing polyisocyanate (a2), an isocyanate is added to the molecular terminal. After obtaining the polyurethane (A-1) having a group, the polyurethane (A-1) having an isocyanate group at the molecular terminal is reacted with the active hydrogen atom-containing (meth) acrylate (a3). A (meth) acryloyl group-containing polyurethane (A) can be produced.

Examples of the aliphatic cyclic structure-containing polyol (a1) include 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanediol, 1,4. -Cyclohexanediol, alicyclic diols such as 2-bis (4-hydroxycyclohexyl) -propane, and the like can be used.
Among them, it is preferable to use an aliphatic cyclic structure-containing polyol (a1-1) having a molecular weight in the range of 100 to 300. Further, when 1,4-cyclohexanedimethanol is used in producing the radical polymerizable resin composition described later, the radical polymerizable unsaturated monomer (C) of the (meth) acryloyl group-containing polyurethane (A) It is more preferable since the solubility of the molded product is improved and further excellent mechanical strength is imparted to the obtained molded product.

Examples of the aliphatic cyclic structure-containing alkylene group or chain alkylene group-containing polyisocyanate (a2) used in the present invention include 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. Aliphatic polyisocyanates such as isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexyl diisocyanate, bis (isocyanatemethylcyclohexane), norbornene diisocyanate and the like, and these nurates are used alone or in combination. be able to.
Among them, the use of isophorone diisocyanate, norbornene diisocyanate, dicyclohexylmethane diisocyanate is useful in the production of a radical polymerizable resin composition to be described later, and the radical polymerizable unsaturated monomer of (meth) acryloyl group-containing polyurethane (A). While the solubility with respect to a body (C) improves, more excellent mechanical strength and light discoloration resistance are provided to the molded product obtained, it is preferable. In particular, it is more preferable to use isophorone diisocyanate or norbornene diisocyanate because the obtained molded product is given further excellent elongation, mechanical strength and heat resistance.

Examples of the active hydrogen atom-containing (meth) acrylate (a3) used in the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate etc. are mentioned. In addition, mono (meth) acrylates of alcohols having two hydroxyl groups such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate; adducts of α-olefin epoxide and (meth) acrylic acid; Addition product of carboxylic acid glycidyl ester and (meth) acrylic acid; di (meth) acrylate of tris (hydroxyethyl) isocyanuric acid, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc .; aminomethyl (meta) ) Acrylate, 2-aminoethyl (meth) acrylate, 3-aminopropyl (meth) acrylate; (meth) acrylic acid, ethylene oxide of (meth) acrylic acid, propylene oxide, tetrahydrofuran No butylene oxide adducts, the hydroxyl group-containing (meth) anhydride adducts of acrylate; and the like. These may be used alone or in combination as long as the effects of the invention are not impaired.
Especially, it is preferable to use a hydroxyl-containing (meth) acrylate, and it is more preferable to use a hydroxyl-containing methacrylate. By using the hydroxyl group-containing methacrylate, the obtained molded product can be made particularly excellent in heat resistance.

The reaction between the aliphatic cyclic structure-containing polyol (a1) and the aliphatic cyclic structure-containing alkylene group or chain alkylene group-containing polyisocyanate (a2) is, for example, the aliphatic cyclic structure-containing alkylene group or Equivalent ratio [isocyanate group of (a2) / hydroxyl group of (a1)] of the isocyanate group of the chain alkylene group-containing polyisocyanate (a2) and the hydroxyl group of the aliphatic cyclic structure-containing polyol (a1) is 1.3. / 1 to 2.5 / 1, preferably 1.5 / 1 to 2/1. Thereby, the polyurethane (A-1) which has an isocyanate group in a molecular terminal can be manufactured.

The reaction between the aliphatic cyclic structure-containing polyol (a1) and the aliphatic cyclic structure-containing alkylene group or chain alkylene group-containing polyisocyanate (a2) is preferably performed in a temperature range of 50 to 110 ° C. More preferably, it is carried out in a temperature range of 60 to 90 ° C.
Moreover, it is preferable that the number average molecular weights of the polyurethane (A-1) which has an isocyanate group in the said molecular terminal are 400-1300, and it is more preferable that it is 400-1000. In order to obtain the number average molecular weight within the above range, the reaction conditions can be appropriately determined. As the reaction conditions, for example, it is preferable to carry out within the above reaction temperature range and use a reaction catalyst in combination as necessary.

Moreover, when manufacturing the polyurethane (A-1) which has an isocyanate group in the said molecular terminal, the radically polymerizable unsaturated monomer (C) and polymerization inhibitor which do not participate in reaction can be used.
A radically polymerizable unsaturated monomer (C) can be used in 5-40 mass% with respect to the polyurethane (A-1) which has an isocyanate group in the said molecular terminal.
The polymerization inhibitor can be used in the range of 10 ppm to 1500 ppm with respect to the polyurethane (A-1) having an isocyanate group at the molecular end.
The reaction between the polyurethane (A-1) having an isocyanate group at the molecular end and the active hydrogen atom-containing (meth) acrylate (a3) is a hydroxyl group of the active hydrogen atom-containing (meth) acrylate (a3). The equivalent ratio of the amino group or the carboxyl group and the isocyanate group remaining in the polyurethane (A-1) having an isocyanate group at the molecular end is active hydrogen equivalent / isocyanate equivalent = 1/1 to 1.3 / 1. It can be performed under conditions that fall within the range. Thereby, the said (meth) acryloyl group containing polyurethane (A) can be manufactured.
The reaction between the polyurethane (A-1) having an isocyanate group at the molecular end and the active hydrogen atom-containing (meth) acrylate (a3) is preferably performed in a temperature range of 50 to 100 ° C.
When manufacturing the said (meth) acryloyl group containing polyurethane (A), well-known catalysts, such as an octyl tin type compound, can be used.
Moreover, when manufacturing the said (meth) acryloyl group containing polyurethane (A), a polymerization inhibitor can be used. Examples of the polymerization inhibitor include those described later. For example, the polymerization inhibitor can be used at 10 to 1500 ppm with respect to the (meth) acryloyl group-containing polyurethane (A).

Examples of the reaction catalyst include organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate; Examples thereof include acids and alkalis such as stannous chloride, stannous bromide and stannous iodide. The amount of these catalysts added is preferably 5 to 10,000 ppm with respect to the total charge.

The (meth) acryloyl group-containing polyurethane (B) used in the present invention has a structure represented by the following general formula (II).

（一般式（ＩＩ）中のＹ´は、炭素原子数２以上であるオキシアルキレン単位を有するポリエーテル骨格を有する構造を表し、前記ポリエーテル骨格部分の平均分子量は３５０以上、Ｔ´は、芳香族構造含有化合物、脂肪族環式構造含有アルキレン基又は鎖状アルキレン基を表し、Ｘは、（メタ）アクリロイル基を含む原子団を表す。）

(Y ′ in the general formula (II) represents a structure having a polyether skeleton having an oxyalkylene unit having 2 or more carbon atoms, the average molecular weight of the polyether skeleton portion is 350 or more, and T ′ is an aromatic Represents a group structure-containing compound, an aliphatic cyclic structure-containing alkylene group or a chain alkylene group, and X represents an atomic group containing a (meth) acryloyl group.

Y ′ in the general formula (II) represents a structure having a polyether skeleton having an oxyalkylene unit having 2 or more carbon atoms as described above, and the average molecular weight of the polyether skeleton portion is 350 or more. Consists of
Examples of the polyether skeleton (b1) include alkylene oxides having 2 or more carbon atoms, and block type polyether skeletons composed of alkylene oxide and ethylene oxide having 3 or more carbon atoms. In the polyether skeleton-containing urethane resin having an oxyalkylene unit having 2 or more carbon atoms, the average molecular weight of the polyether skeleton portion is 350 or more. However, when the polyether skeleton-containing urethane resin has a plurality of polyether skeleton portions in the molecule, the average molecular weight may be an average molecular weight obtained by summing the plurality of polyether skeleton portions.

The (meth) acryloyl group-containing polyurethane (B) is, for example, a polyether polyol having an oxyalkylene unit having 2 or more carbon atoms, a polyisocyanate (b2), an active hydrogen atom-containing (meth) acrylate (b3), Can be made to react.

As the polyether skeleton (b1), a polyether polyol having an oxyalkylene unit having 2 or more carbon atoms can be used. This polyether polyol is a polyhydric alcohol having a polyether skeleton, provided that the polyether skeleton has an oxyalkylene unit having 2 or more carbon atoms. The oxyalkylene units polyether polyol has, for example, _{-O-CH 2} -CH 2 - ethylene oxide represented _{by, -O-CH 2 -CH (CH} 3) - propylene oxide represented by, -O- ( CH _{2) 4} - tetramethylene oxide represented _{by, -O-CH 2 -CH (CH} 2 Cl) - 3- chloro-propylene oxide represented by like include alkylene oxides such as of 2 to 4 carbon atoms. The oxyalkylene unit contained in the polyether polyol is more preferably propylene oxide, which is an alkylene oxide having 3 or more carbon atoms.

The polyether skeleton-containing urethane resin used in the present invention has an average molecular weight of 350 or more in the polyether skeleton portion.

The polyether polyol having an oxyalkylene unit having 2 or more carbon atoms may be a polyhydric alcohol containing an oxyalkylene unit having 2 or more carbon atoms. That is, in addition to the use of polypropylene glycol or the like as the polyether polyol, polyethylene oxide (EO) -polypropylene which is a polyhydric alcohol containing an oxyalkylene unit having 3 or more carbon atoms and an oxyethylene unit. Oxide (PO) -block polymers, specifically, EO-PO-EO glycol (terminal EO glycol) and PO-EO-PO glycol (terminal PO glycol) can be used. As the polyether polyol, the above polyethylene oxide-polypropylene oxide-block polymer can also be used.

T ′ in the general formula (II) represents an aromatic structure-containing compound, an aliphatic cyclic structure-containing alkylene group or a chain alkylene group, and includes a structure derived from polyisocyanate (b2) described later.
Examples of the polyisocyanate (b2) used in the (meth) acryloyl group-containing polyurethane (B) include aliphatic or aliphatic such as hexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, hydrogenated xylylene diisocyanate, and dicyclohexylmethane diisocyanate. Diisocyanates having aromatic systems such as cyclic diisocyanate, 2,4-tolylene diisocyanate, xylylene diisocyanate, tolidine diisocyanate, naphthylene diisocyanate, and isomers of these polyisocyanates; for example, isomerism such as 4,4-diphenylmethane diisocyanate Or mixtures of these polyisocyanates and isomers of these polyisocyanates, triphenylmethane triisocyanate And the like can be used. Of these polyisocyanates, diisocyanates are preferred. These polyisocyanates can be used alone or in combination.

X in the general formula (II) is an atomic group containing a (meth) acryloyl group, and includes a structure derived from an active hydrogen atom-containing (meth) acrylate similar to X in the general formula (I). And described as active hydrogen atom-containing (meth) acrylate (b3).
Examples of the active hydrogen atom-containing (meth) acrylate (b3) used in the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate etc. are mentioned. In addition, mono (meth) acrylates of alcohols having two hydroxyl groups such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate; adducts of α-olefin epoxide and (meth) acrylic acid; Addition product of carboxylic acid glycidyl ester and (meth) acrylic acid; di (meth) acrylate of tris (hydroxyethyl) isocyanuric acid, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc .; aminomethyl (meta) ) Acrylate, 2-aminoethyl (meth) acrylate, 3-aminopropyl (meth) acrylate; (meth) acrylic acid, ethylene oxide of (meth) acrylic acid, propylene oxide, tetrahydrofuran No butylene oxide adducts, the hydroxyl group-containing (meth) anhydride adducts of acrylate; and the like. These may be used alone or in combination as long as the effects of the invention are not impaired.
Especially, it is preferable to use a hydroxyl-containing (meth) acrylate, and it is more preferable to use a hydroxyl-containing methacrylate. By using the hydroxyl group-containing methacrylate, the obtained molded product can be made particularly excellent in heat resistance.

The reaction between the polyether skeleton (b1) and the polyisocyanate (b2) is, for example, an equivalent ratio of the isocyanate group of the polyisocyanate (b2) and the hydroxyl group of the polyether skeleton (b1) [(b2) The isocyanate group / (b1) hydroxyl group] is 1.3 / 1 to 2.5 / 1, preferably 1.5 / 1 to 2/1. Thereby, the polyurethane (B-1) which has an isocyanate group in a molecular terminal can be manufactured.

The reaction between the polyether skeleton (b1) and the polyisocyanate (b2) is preferably performed in a temperature range of 50 to 110 ° C, and more preferably in a temperature range of 60 to 90 ° C.
Moreover, it is preferable that the number average molecular weights of the polyurethane (B-1) which has an isocyanate group in the said molecular terminal are 700-4000, and it is more preferable that it is 1000-3000. In order to obtain the number average molecular weight within the above range, the reaction conditions can be appropriately determined.
As the reaction conditions, for example, it is preferable to carry out within the above reaction temperature range and use a reaction catalyst in combination as necessary.
Moreover, when manufacturing the polyurethane (B-1) which has an isocyanate group in the said molecular terminal, using the above-mentioned radically polymerizable unsaturated monomer (C) which does not participate in reaction, or the above-mentioned polymerization inhibitor. it can.

The reaction between the polyurethane (B-1) having an isocyanate group at the molecular end and the active hydrogen atom-containing (meth) acrylate (b3) is a hydroxyl group of the active hydrogen atom-containing (meth) acrylate (b3), The equivalent ratio of the amino group or the carboxyl group and the isocyanate group remaining in the polyurethane (B-1) having an isocyanate group at the molecular end is such that the active hydrogen equivalent / isocyanate equivalent = 1/1 to 1.3 / 1. It can be performed under conditions that fall within the range. Thereby, the said (meth) acryloyl group containing polyurethane (B) can be manufactured.
The reaction between the polyurethane (B-1) having an isocyanate group at the molecular terminal and the active hydrogen atom-containing (meth) acrylate (b3) is preferably performed in a temperature range of 50 to 100 ° C.
When manufacturing the said (meth) acryloyl group containing polyurethane (B), well-known catalysts, such as an octyl tin type compound, can be used.
Moreover, when manufacturing the said (meth) acryloyl group containing polyurethane (B), a polymerization inhibitor can be used. Examples of the polymerization inhibitor include those described later. For example, the polymerization inhibitor can be used at 10 to 1500 ppm with respect to the (meth) acryloyl group-containing polyurethane (B).

Examples of the catalyst include organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate; organic tin compounds such as tin octylate, dibutyltin oxide, dibutyltin laurate, and dibutyltin diversate; Examples of the compound include acids and alkalis such as stannous chloride, stannous bromide, and stannous iodide. The amount of these catalysts added is preferably 5 to 10,000 ppm with respect to the total charge.

Moreover, it is preferable to contain 10-100 mass parts of said (meth) acryloyl group containing polyurethanes (B) with respect to 100 mass parts of said (meth) acryloyl group containing polyurethanes (A).
For example, with the (meth) acryloyl group-containing polyurethane (A) alone, the cured product obtained has an insufficient elongation and heat resistance is maintained, but the physical properties of the cured product tend to be somewhat brittle. On the other hand, when the (meth) acryloyl group-containing polyurethane (B) alone is used, the heat resistance of the resulting cured product is lowered, and when the content of the (meth) acryloyl group-containing polyurethane (B) exceeds the above range, The heat resistance and mechanical strength of the resulting cured product may be reduced. Therefore, the radical polymerizable resin composition of the present invention needs to contain the (meth) acryloyl group-containing polyurethane (A) and the (meth) acryloyl group-containing polyurethane (B) within the above range. .

Examples of the radical polymerizable unsaturated monomer (C) include styrene, α-methylstyrene, chlorostyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, vinyltoluene, vinyl acetate, diarylphthalate, and triaryl. (Iso) cyanurate; further, as an acrylate ester, a methacrylate ester, etc., methyl (meth) acrylate (methyl methacrylate), ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, T-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic Tridecyl acid, dicyclopenteni Oxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monobutyl ether (meth) acrylate, ethylene glycol monohexyl ether (meth) acrylate, ethylene glycol mono 2-ethylhexyl Ether (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monobutyl ether (meth) acrylate, diethylene glycol monohexyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate Dipropylene Recall monomethyl ether (meth) acrylate, dipropylene glycol monoethyl ether (meth) acrylate, dipropylene glycol monobutyl ether (meth) acrylate, dipropylene glycol monohexyl ether (meth) acrylate, dipropylene glycol mono 2-ethylhexyl ether (meth) ) Acrylate, phenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono ( (Meth) acrylate, polypropylene glycol mono (meth) acrylate, isocyanuric acid di (meth) acrylate, pentaeryth Tall tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, aminomethyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 3-aminopropyl (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, polytetramethylene ether glycol (PTMG) di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di ( (Meth) acrylate, 2-hydroxy-1,3-dimethacryloxypropane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxydiethoxy) Enyl] propane, 2,2-bis [4- (methacryloxy-polyethoxy) phenyl] propane, tetraethylene glycol di (meth) acrylate, ethylene oxide (EO) modification of bisphenol A (n = 1-8) di (meth) Acrylate, ethylene oxide (EO) modification of isocyanuric acid (EO) (n = 1-3) di (meth) acrylate, ethylene oxide (EO) modification of isocyanuric acid (n = 1-3), tri (meth) acrylate, pentaerythritol di ( A polymerizable unsaturated compound capable of crosslinking with a resin, such as a (meth) acrylate monoester, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate, can be used.

The radical polymerizable unsaturated monomer (C) is the radical polymerizable unsaturated monomer (A) based on the total of the (meth) acryloyl group-containing polyurethane (A) and the (meth) acryloyl group-containing polyurethane (B). It is preferable to use in a range where the mass ratio [((A) + (B)) / (C)] of C) is 70/30 to 30/70.

The radical polymerizable resin composition is prepared by heating or the like, the (meth) acryloyl group-containing polyurethane (A) and the (meth) acryloyl group-containing polyurethane (B) have the (meth) acryloyl group and the radical polymerizable unsaturated. Organic peroxide (E) that proceeds the radical polymerization with the unsaturated group of the monomer (C) to obtain a molded product having excellent mechanical strength, heat resistance, etc. More preferably, is used.

Examples of the organic peroxide (E) include diacyl peroxides, peroxyesters, hydroperoxides, dialkyl peroxides, ketone peroxides, peroxyketals, alkyl peresters, and carbonates. Known systems such as systems can be used.
The organic peroxide (E) includes the (meth) acryloyl group-containing polyurethane (A), the (meth) acryloyl group-containing polyurethane (B) constituting the radical polymerizable resin composition, and the radical polymerizable non-polymerizable. It is preferable to use in the range of 0.1 to 10 parts by mass, and more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass in total with the saturated monomer (C).

In addition to the organic peroxide (E), an ultraviolet curing agent, an electron beam curing agent, or the like may be used in combination with the radical polymerizable resin composition of the present invention within a range that does not impair the effects of the present invention. Good.
Examples of the ultraviolet curing agent that can be used include acylphosphine oxide, benzoin ether, benzophenone, acetophenone, and thioxanthone compounds.
Moreover, as an electron beam hardening | curing agent, halogenated alkylbenzene, a disulfide type compound, etc. can be used, for example.

The radically polymerizable resin composition of the present invention, for example, produces the (meth) acryloyl group-containing polyurethane (A) and the (meth) acryloyl group-containing polyurethane (B) by the method described above, and then the (meth) acryloyl group. It can be produced by mixing and stirring the containing polyurethane (A) and the (meth) acryloyl group-containing polyurethane (B) and the radical polymerizable unsaturated monomer (C). Alternatively, the (meth) acryloyl group-containing polyurethane (A) and the (meth) acryloyl group-containing polyurethane (B) may be prepared by using the respective polyol component, polyisocyanate component and active hydrogen atom-containing (meth) acrylate. (A) or polyurethane (B) can be used by batch production by the same method as the production method.
When the organic peroxide (E) is used, the (meth) acryloyl group-containing polyurethane (A) and (meth) acryloyl group-containing polyurethane (B), the radical polymerizable unsaturated monomer (C), In mixing the organic peroxide (E), the (meth) acryloyl group-containing polyurethane (A) and the (meth) acryloyl group-containing polyurethane (B), and the radical polymerizability may be used. It is preferable to mix and use the organic peroxide (E) with respect to the radical polymerizable resin composition obtained by previously mixing the unsaturated monomer (C).
You may perform the said mixing using apparatuses, such as a stirrer, a kneader, a roll mill, a screw extrusion type kneader, for example.

The viscosity of the radical polymerizable resin composition of the present invention is preferably in the range of 0.5 to 50 dPa · s, particularly preferably in the range of 0.7 to 20 dPa · s.
The viscosity of the radical polymerizable resin composition can be measured using a known device or the like according to JIS-K-6901.

A polymerization inhibitor, a curing accelerator and the like can be added to the radical polymerizable resin composition of the present invention as necessary.
Examples of the polymerization inhibitor include toluhydroquinone, hydroquinone, hydroquinone monomethyl ether, 1,4-naphthoquinone, parabenzoquinone, toluhydronone, p-tert-butylcatechol, 2,6-tert-butyl-4-methylphenol. 1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol, 4-hydroxy-2,2,6,6 -N-oxyl compounds such as tetramethylpiperidine-1-oxyl can be used.
The amount of the polymerization inhibitor used is preferably 10 to 1500 ppm in the radical polymerizable resin composition.

Examples of the curing accelerator include metal soaps such as cobalt naphthenate, cobalt octenoate, vanadyl octenoate, copper naphthenate, and barium naphthenate; metal chelates such as vanadyl acetyl acetate, cobalt acetyl acetate, and iron acetylacetonate. Compound; N, N-dimethylamino-p-benzaldehyde, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p -Toluidine, 4-N, N-dimethylaminobenzaldehyde, 4-N, N-bis (2-hydroxyethyl) aminobenzaldehyde, 4-methylhydroxyethylaminobenzaldehyde, N, N-bis (2-hydroxypropyl) -p -Toluidine, N-ethyl-m-toluidine , Triethanolamine, m- toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, it is also possible to use by adding a small amount of compounds such as diethanol aniline.

Glass fiber or carbon fiber can be used as the radically polymerizable resin composition of the present invention and the fiber reinforcing material (D) to be cured.
Each of the glass fiber and the carbon fiber may be, for example, a twisted yarn, a spun yarn, a spun yarn, a non-woven fabric, and specifically, a filament, a yarn, a roving, a strand, a chopped strand, a felt, a needle punch, Examples of the shape include cloth, roving cloth, and milled fiber.
As the carbon fiber, a polyacrylonitrile (PAN) -based, rayon-based, pitch-based carbon fiber or the like subjected to a sizing treatment with a sizing agent is used. Each of the carbon fibers is produced by spinning by a known method, flame resistance (infusibilization), carbonization, and, if necessary, graphitization treatment. Usually, these carbon fibers are supplied as strands in which 1000 to 50000 filaments are bundled. Among these carbon fibers, in the present invention, it is particularly preferable to use a PAN-based carbon fiber excellent in handleability, manufacturing process passability, and molded product strength. From the viewpoint of rigidity strength, so-called pitch-based carbon fiber is used. It is preferable to use fibers.
Here, the PAN-based carbon fiber is based on a copolymer containing acrylonitrile structural units as a main component and containing 10 mol% or less of a vinyl monomer unit such as itaconic acid, acrylic acid, acrylic ester, and acrylamide, This is a fiber that has been made flame resistant by heat treatment in an oxidizing atmosphere and then carbonized or graphitized in an inert atmosphere.
Further, the carbon fiber may be subjected to surface treatment such as electrolytic acid value treatment in advance separately from the bundling treatment.
As the bundling agent used for bundling carbon fibers, those containing an aromatic structure and an unsaturated double bond-containing resin are used.

In addition, the radical polymerizable resin composition includes, as necessary, conventionally known unsaturated polyester resins, vinyl urethane resins, vinyl ester resins, diallyl phthalate resins, polyisocyanates, polyepoxides, acrylic resins. , Alkyd resins, urea resins, melamine resins, polyvinyl acetate, vinyl acetate copolymers, polydiene elastomers, saturated polyesters, saturated polyethers; rubber materials such as NBR, nitrocellulose, cellulose acetate buty Other conventional natural and synthetic polymer compounds such as cellulose derivatives such as rate; oils and fats such as linseed oil, tung oil, soybean oil, castor oil, epoxidized oil, etc. can be added.
The radical polymerizable resin composition includes organic fibers such as glass fiber, carbon fiber, aramid fiber, vinylon fiber, and tetron fiber, metal fibers, nanofibers composed thereof, natural plant fibers such as jute and manila hemp, carbonic acid Fillers such as calcium, talc, mica, clay, silica powder, colloidal silica, barium sulfate, aluminum hydroxide, glass powder, glass beads, and crushed sand can be blended and used.
Furthermore, the radical polymerizable resin composition includes zinc stearate, titanium white, zinc white, various other pigment stabilizers, flame retardants, antifoaming agents, coupling agents, internal mold release agents, thermoplastic resins and the like. Use other additives such as compatibilizers, anti-aging agents, plasticizers, aggregates, flame retardants, light stabilizers, heat stabilizers etc. can do.

The radical-polymerizable resin composition of the present invention includes various moldings such as hand lay-up, spray-up molding, RTM (resin transfer molding) molding, vacuum infusion molding, continuous molding, pultrusion molding, filament winding molding, and injection molding. Molded by the method, a molded product can be obtained. Further, fillers, additives, and the like can be added to the radical polymerizable resin composition to use as a so-called compound. Using this compound, so-called sheet molding compound (SMC) in which the compound is formed into a sheet by press molding. A molded product can be obtained by a molding method according to each application, such as press molding by using a so-called bulk molding compound (BMC) in which the compound is bulked, injection molding, transfer molding, or the like. Moreover, it is also possible to use the radically polymerizable resin composition as a paint by coating and curing with a thin film.

Although the curing reaction of the radical polymerizable resin composition varies depending on the type of the organic peroxide (E) to be used, etc., it is preferably carried out by heating at about room temperature to 150 ° C.

Moreover, the radically polymerizable resin composition of this invention can be utilized for a block-shaped molding material and a sheet-shaped molding material, that is, it can be applied to bulk molding or sheet molding. At that time, it is necessary to thicken the compound. Conventionally, for example, a metal oxide such as magnesium oxide is suitably used for SMC, BMC, etc. as a thickener.
In the present invention, as a thickener (F), acrylic resin fine particles can be obtained from the viewpoint of obtaining a block-shaped molding material and a sheet-shaped molding material having better viscosity and excellent handleability, moldability, and strength. It is preferable to use a thickener using powder.

As said thickener (F), the powdery thing which has polymethyl methacrylate or methyl methacrylate as a main component can be used.
As a monomer constituting polymer powder containing methyl methacrylate as a main component, acrylic ester or methacrylic ester includes, for example, ethyl (meth) acrylate, n-butyl (meth) acrylate, methyl methacrylate, butyl (meth) acrylate. , N-propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl methacrylate, isobutyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, Examples thereof include n-octyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate. Examples of the diene monomer include conjugated diene compounds such as butadiene, isoprene, 1,3-pentadiene, cyclopentadiene and dicyclopentadiene, and non-conjugated diene compounds such as 1,4-hexadiene and ethylidene norbornene. It can also be used. In addition, monomers copolymerizable with these include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, pt-butylstyrene, chlorostyrene, acrylamide, N-methylolacrylamide, and N-butoxymethyl. Mention may also be made of acrylamide compounds such as acrylamide, methacrylamide compounds such as methacrylamide, N-methylol methacrylamide and N-butoxymethyl methacrylamide, and glycidyl acrylate, glycidyl methacrylate, allyl glycidyl acrylate and the like.
In the polymer powder containing methyl methacrylate as a main component, a crosslinkable monomer having at least two double bonds capable of radical polymerization with an acrylate or methacrylate ester monomer can be used. . Specific examples include ethylene glycol diacrylate, butylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, hexanediol diacrylate, oligoethylene diacrylate, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, trimethylol. Examples include propanedimethacrylate, trimethylolpropane trimethacrylate, hexanediol dimethacrylate, oligoethylene dimethacrylate, aromatic divinyl monomers such as divinylbenzene, triallylic acid triallyl, triallyl isocyanurate, and the like. However, the amount of the crosslinkable monomer in the polymer powder preferably does not exceed 0.5% by weight. This is because the degree of crosslinking becomes too high and does not swell in the component as a matrix resin. In this case, the acrylic powder remains as an insoluble part, and the strength of the resulting molded product is inferior.

The method for producing the polymer powder is not particularly limited, but is usually produced by emulsion polymerization. That is, an emulsion is obtained by subjecting a monomer as a component to emulsion polymerization using a radical polymerization initiator such as a peroxide initiator or a redox initiator as a polymerization initiator in the presence of an emulsifier. By such emulsion polymerization, an emulsion containing a particulate copolymer having a particle size of preferably 300 to 5000 angstroms is produced.
The emulsion containing the copolymer obtained by emulsion polymerization is usually spray-dried by a multiblade rotating disk type, a disk type rotating disk type, a nozzle type or the like to obtain a powdery copolymer. In the case of this spray drying, the copolymer generally aggregates in units of spray droplets, and preferably forms aggregated particles of about 20 to 100 μm. The degree of aggregation varies depending on the drying conditions, and a step of pulverizing and loosening the aggregated particles after spray drying can be provided. Alternatively, after the emulsion polymerization, latex particles are coagulated and separated by a salting-out method or a freezing method, and a wet cake prepared by dehydration can be dried in a fluidized bed to obtain aggregated particles.

It is preferable that the said thickener (F) which is the said polymer powder is the range of 1-150 weight part with respect to 100 weight part of radically polymerizable resin compositions of this invention. More preferably, it is the range of 10-40 weight part. This is because if the amount is less than 1 part by weight, the thickening is insufficient and problems such as stickiness occur in handling. When the amount exceeds 150 parts by weight, the viscosity becomes high immediately after the addition, which makes it difficult to knead, or even when kneading is possible, the polymer powder remains as an insoluble matter after thickening, and the texture of the molded product is impaired. This is because. The radical polymerizable resin composition with increased viscosity can be used as a molding material that can be used in various applications as well as having further excellent physical properties by further including additives such as fillers and reinforcing materials. it can.

An example of a method for producing a molding material using the radically polymerizable resin composition of the present invention will be outlined below, taking sheet and block forms as examples, but the present invention is limited to this production method. is not.

When the radically polymerizable resin composition is a sheet-like prepreg, the radically polymerizable resin composition may be prepared by using a known mixer such as a planetary mixer or a kneader, an inorganic filler, an internal mold release, and the like. An agent, a dispersant, and finally a thickener (F) which is a polymer mainly composed of polymethyl methacrylate or methyl methacrylate are added and mixed and stirred.
The compound prepared in the mixer is applied to one or both of the two release films with a flow coater or doctor knife, preferably to a constant thickness of 0.3-5 mm. If necessary, the fiber reinforcing material (D) is cut with a chopper and sprayed on the coated surface, or a mat reinforcing material composed of the fiber reinforcing material (D) is sandwiched between the two coated surfaces. After that, they are bonded together and rolled by a rolling mill to obtain a sheet having a thickness of preferably 0.5 to 7 mm. The sheet is wound or folded with a roller while both sides of the sheet are covered with a release film. Further, as a case where an SMC machine is not particularly used, for example, a chopped strand mat may be impregnated with the above compound with a roll or the like.
The thickening process varies depending on the type, amount and temperature of the thickener (F), but it is preferably performed at room temperature (25 ° C.) for 1 hour and by heating at 45 ° C. for 30 minutes. The obtained prepreg has good release properties of the release film as a sheet-shaped molding material.

When the radical polymerizable resin composition is used as a bulk premix, carbon fiber powder is used for the radical polymerizable resin composition by using a known mixer such as a planetary mixer or a kneader. Alternatively, milled fiber made of carbon fiber, inorganic filler, internal mold release agent, dispersant, and finally thickener (F) are added and mixed and stirred.
Moreover, when using a fiber reinforcement (D), it is preferable to use immediately after adding a thickener (F). The mixed composition is removed into a polyethylene bag and sealed. As in the case of the prepreg, the composition is thickened by normal temperature and heating. The shape of the premix can be various shapes and sizes such as pellets, pebbles, bricks, etc., but usually the diameter or one side is preferably 0.7 cm to 1 m.
The thickening process varies depending on the type, amount, and temperature of the thickener (F), but is adjusted so that it can be performed at room temperature (25 ° C.) for 1 hour and by heating at 45 ° C. in 30 minutes. The obtained premix has little stickiness as a block-shaped molding material and is very easy to handle.

The sheet-like molding material and block-like molding material thus obtained are usually heated in the mold by a compression heating molding method at a pressure of 1 to 20 MPa using a mold having a temperature range of about 100 ° C to 150 ° C. It is shaped and manufactured as a carbon fiber reinforced plastic or molded product.

The molded product of the present invention utilizes, for example, characteristics that can achieve both high toughness and heat resistance. For example, automobile-related parts such as automobile outer plates and vehicle platform members, pressure pipes, pressure vessels, blades for wind power generation, boats, water It can be used as a core material that can be used when winding a motorcycle, a railway vehicle member, an aircraft member, a building member for seismic reinforcement, an industrial robot, an SMC, or the like.

Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to these examples. In the following, “part” and “%” are based on mass unless otherwise specified.

Synthesis Example 1 Synthesis of Polyurethane (I) A 2-liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet and reflux condenser, 202 parts of 1,4-cyclohexanedimethanol and isophorone 622 parts of diisocyanate was charged and stirred at 90 ° C. for about 2 hours to obtain a polyurethane having an isocyanate group at the molecular end.
Thereafter, 382 parts of 2-hydroxyethyl methacrylate, 50 ppm of tin-based catalyst and 50 ppm of toluhydroquinone were added and reacted at 90 ° C. for about 7 hours to obtain polyurethane (I) having a molecular weight of 848.
The molecular weight is a value obtained by calculation based on the formula weight of the atoms constituting the polyurethane (I).

Moreover, the polyurethane (I) obtained in Example 1 was identified by the measurement of IR spectrum on the following conditions. The IR spectrum is shown in FIG. In FIG. 1, the horizontal axis represents the wavelength (cm ⁻¹ ), and the peaks in the spectrum are as follows.
(IR spectrum measurement conditions)
Measuring instrument: Infrared spectrophotometer FT / IR-460 (manufactured by JASCO Corporation).
Measurement method: Transmission method using KBr plate.
Integration count: 16 times.
(Peak attribution)
[Peak derived from cyclohexanedimethanol]
^{2920cm -1, 2860cm -1, 1450cm -1} : C-H vibrations.
1030 cm ⁻¹ : C—O absorption.
[Peak of confirmation of urethane bond formation]
1710cm ^-1: C = O group ^{1530cm -1: ~N (H) -C} = O~.
[Peak confirming disappearance of isocyanate group]
2260-2270 cm < ^-1 >: NCO group.

(Synthesis Example 2) Synthesis of Polyurethane (II) 216 parts of cyclohexanedimethanol and 618 parts of norbornene diisocyanate were charged in the same reactor as in Synthesis Example 1, and stirred at 80 ° C. for about 2 hours. A polyurethane having an isocyanate group was obtained.
Thereafter, 410 parts of 2-hydroxyethyl methacrylate, 50 ppm of a tin-based catalyst and 50 ppm of toluhydroquinone were added and reacted at 90 ° C. for about 7 hours to obtain polyurethane (II) having a molecular weight of 816.
The molecular weight is a value obtained by calculation based on the formula weight of the atoms constituting the polyurethane (II).

(Synthesis Example 3) Synthesis of Polyurethane (III) In the same reactor as in Synthesis Example 1, 805 parts of polypropylene glycol (molecular weight calculated from hydroxyl value 1518), 4,4'-diphenylmethane diisocyanate and 2,2'- 265 parts of a mixture of diphenylmethane diisocyanate was charged, and heated and stirred at 80 ° C. for about 2 hours to obtain a polyurethane having an isocyanate group at the molecular end (isocyanate equivalent 1009).
Thereafter, 160 parts of 2-hydroxypropyl methacrylate, 40 ppm of a tin-based catalyst and 50 ppm of toluhydroquinone were added and reacted at 90 ° C. for about 3 hours to obtain polyurethane (III).

(Synthesis Example 4) Synthesis of Polyurethane (IV) In the same reaction apparatus as in Synthesis Example 1, 877 parts of polypropylene glycol (molecular weight calculated from hydroxyl value 1993), 4,4'-diphenylmethane diisocyanate and 2,2'- 220 parts of a mixture of diphenylmethane diisocyanate was charged and stirred with heating at 80 ° C. for about 2 hours to obtain a polyurethane having an isocyanate group at the molecular end (isocyanate equivalent 1247).
Thereafter, 133 parts of 2-hydroxypropyl methacrylate, 40 ppm of a tin-based catalyst and 50 ppm of toluhydroquinone were added and reacted at 90 ° C. for about 3 hours to obtain polyurethane (IV).

(Synthesis Example 5) Synthesis of Polyurethane (V) In the same reaction apparatus as in Synthesis Example 1, 412 parts of polypropylene glycol (molecular weight 404 calculated from hydroxyl value), 4,4'-diphenylmethane diisocyanate and 2,2'- A mixture of diphenylmethane diisocyanate (510 parts) was charged and heated and stirred at 80 ° C. for about 2 hours to obtain a polyurethane having an isocyanate group at the molecular end (isocyanate equivalent 450).
Thereafter, 308 parts of 2-hydroxypropyl methacrylate, 40 ppm of a tin-based catalyst and 50 ppm of toluhydroquinone were added and reacted at 90 ° C. for about 3 hours to obtain polyurethane (V).

(Synthesis Example 6) Synthesis of Unsaturated Polyester In the same reactor as in Synthesis Example 1, 263 parts of propylene glycol, 190 parts of ethylene glycol, 533 parts of phthalic anhydride, and 235 parts of maleic anhydride were charged in a nitrogen atmosphere. The temperature was raised to 220 ° C. and reacted for about 7 hours. When the solid acid value reached 18.4, after cooling to 170 ° C., 100 ppm of hydroquinone was added to obtain an unsaturated polyester.

(Synthesis example 7) Synthesis of epoxy methacrylate In the same reaction apparatus as synthesis example 1, 830 parts of bisphenol A epoxy resin (epoxy equivalent 187), 365 parts of methacrylic acid, 350 ppm of dibutylhydroxytoluene, 2-methylimidazole Was reacted at 110 ° C. for about 5 hours. When the acid value reached 4, the reaction was terminated to obtain an epoxy methacrylate resin.

(Synthesis Example 8) Synthesis of Polyurethane (VI) 701 parts of polypropylene glycol (molecular weight 701 calculated from hydroxyl value), 296 parts of tolylene diisocyanate, and 67 parts of isophorone diisocyanate are charged in the same reactor as in Synthesis Example 1. The mixture was heated and stirred at 80 ° C. for about 5 hours to obtain a polyurethane having an isocyanate group at the molecular end (isocyanate equivalent 532).
Thereafter, 273 parts of 2-hydroxyethyl methacrylate was added and reacted at 80 ° C. for about 4 hours to obtain polyurethane (VI).

Synthesis Example 9 Synthesis of Polyurethane (VII) In the same reactor as in Synthesis Example 1, 624 parts of bisphenol A-EO 8 mol adduct (molecular weight 693 calculated from hydroxyl value), 4,4′-diphenylmethane diisocyanate and 2 , 2′-diphenylmethane diisocyanate 450 parts was charged and stirred at 80 ° C. for about 2 hours to obtain a polyurethane having an isocyanate group at the molecular end (isocyanate equivalent 597).
Thereafter, 246 parts of 2-hydroxyethyl methacrylate, 50 ppm of a tin-based catalyst and 50 ppm of toluhydroquinone were added and reacted at 90 ° C. for about 3 hours to obtain polyurethane (VII).

Example 1
46 parts of the polyurethane (I) obtained in Synthesis Example 1, 14 parts of the polyurethane (III) obtained in Synthesis Example 3 and 40 parts of styrene monomer were mixed to obtain a uniform solution to obtain a radical polymerizable resin composition.
Using the obtained radical polymerizable resin composition, a cast plate was obtained according to the following cast plate preparation method.
The mechanical properties and heat distortion temperature of the resulting cast plate were measured, and the moldability and punching shear were evaluated. The results are shown in Table 1.

(Example 2)
46 parts of polyurethane (II) obtained in Synthesis Example 2, 14 parts of polyurethane (IV) obtained in Synthesis Example 4 and 40 parts of styrene monomer were mixed to obtain a uniform solution, thereby obtaining a radical polymerizable resin composition.
Except for using the obtained radical polymerizable resin composition, a casting plate was produced in the same manner as in Example 1, and the mechanical properties and thermal deformation temperature of the resulting casting plate were measured. Punching shear was evaluated. The results are shown in Table 1.

(Example 3)
41 parts of the polyurethane (I) obtained in Synthesis Example 1, 9 parts of the polyurethane (III) obtained in Synthesis Example 3 and 50 parts of 2-hydroxyethyl methacrylate were mixed to form a homogeneous solution. Obtained.
Except for using the obtained radical polymerizable resin composition, a casting plate was produced in the same manner as in Example 1, and the mechanical properties and thermal deformation temperature of the resulting casting plate were measured. Punching shear was evaluated. The results are shown in Table 1.
Further, to 100 parts of the radical polymerizable resin composition obtained in Example 3, 0.3 part of 8% cobalt octenoate as an accelerator was added and mixed uniformly, and a radical curing agent (“328E”) was further mixed. A resin composition prepared by adding 1 part of an organic peroxide manufactured by Kayaku Akzo Co., Ltd. was mixed with a carbon fiber cloth (“Pyrofil TR3110MS” on a 350 mm × 350 mm glass plate subjected to a release treatment. (Carbon fiber for vinyl ester resin, manufactured by Mitsubishi Rayon Co., Ltd.) and laminated so that the volume content of carbon fiber is 50% by a hand lay-up molding method (8 ply), and at room temperature (25 ° C.) for 12 hours After curing, it was further cured at 60 ° C. for 3 hours, and the compression strength and compression modulus were measured and evaluated. The results are shown in Table 3 as Example 3-FRP.

Example 4
46 parts of polyurethane (I) obtained in Synthesis Example 1, 14 parts of polyurethane (III) obtained in Synthesis Example 3, 20 parts of 2-hydroxyethyl methacrylate, and 20 parts of methyl methacrylate were mixed to form a homogeneous solution, and radical polymerization was performed. A functional resin composition was obtained.
Except for using the obtained radical polymerizable resin composition, a casting plate was produced in the same manner as in Example 1, and the mechanical properties and thermal deformation temperature of the resulting casting plate were measured. Punching shear was evaluated. The results are shown in Table 1.
Further, to 100 parts of the radical polymerizable resin composition obtained in Example 4, 0.3 part of 8% cobalt octenoate as an accelerator was added and mixed uniformly, and further a radical curing agent (“328E”). A resin composition prepared by adding 1 part of an organic peroxide manufactured by Kayaku Akzo Co., Ltd. was mixed with a carbon fiber cloth (“Pyrofil TR3110MS” on a 350 mm × 350 mm glass plate subjected to a release treatment. (Carbon fiber for vinyl ester resin, manufactured by Mitsubishi Rayon Co., Ltd.) and laminated so that the volume content of carbon fiber is 50% by a hand lay-up molding method (8 ply), and at room temperature (25 ° C.) for 12 hours After curing, it was further cured at 60 ° C. for 3 hours, and the compression strength and compression modulus were measured and evaluated. The results are shown in Table 3, Example 4-FRP.

(Example 5)
46 parts of the polyurethane (I) obtained in Synthesis Example 1, 14 parts of the polyurethane (V) obtained in Synthesis Example 5 and 40 parts of the styrene monomer were mixed to obtain a uniform solution to obtain a radical polymerizable resin composition.
Except for using the obtained radical polymerizable resin composition, a casting plate was produced in the same manner as in Example 1, and the mechanical properties and thermal deformation temperature of the resulting casting plate were measured. Punching shear was evaluated. The results are shown in Table 1.

(Comparative Example 1)
The unsaturated polyester obtained in Synthesis Example 6 was diluted with a styrene monomer so that the non-volatile component was 65% to obtain a radical polymerizable resin composition.
Except for using the obtained radical polymerizable resin composition, a casting plate was produced in the same manner as in Example 1, and the mechanical properties and thermal deformation temperature of the resulting casting plate were measured. Punching shear was evaluated. The results are shown in Table 2.
Further, 100 parts of the radical polymerization composition obtained in Comparative Example 1 was mixed with 0.3 part of 8% cobalt octenoate as an accelerator and mixed uniformly. Further, a radical curing agent (“328E”, A resin composition prepared by adding 1 part of an organic peroxide (manufactured by Yakuzo Akzo Co., Ltd.) and mixing the resulting mixture on a 350 mm × 350 mm glass plate subjected to a release treatment, is made of carbon fiber cloth (“Pyrofil TR3110MS”, Mitsubishi Rayon). (Carbon fiber for vinyl ester resin, manufactured by the company) by a hand lay-up molding method (8 ply) so that the volume content of carbon fiber is 50% and cured at room temperature (25 ° C.) for 12 hours. Then, it was further post-cured at 60 ° C. for 3 hours, and the compression strength and compression modulus were measured and evaluated. The results are shown in Table 3 as Comparative Example 1-FRP. Comparative Example 1-FRP had a lower strength value compared to Example 3-FRP and Example 4-FRP.

(Comparative Example 2)
The epoxy methacrylate resin obtained in Synthesis Example 7 was diluted with a styrene monomer so that the non-volatile component would be 75% to obtain a radical polymerizable resin composition.
Except for using the obtained radical polymerizable resin composition, a casting plate was produced in the same manner as in Example 1, and the mechanical properties and thermal deformation temperature of the resulting casting plate were measured. Punching shear was evaluated. The results are shown in Table 2.
Further, 100 parts of the radical polymerization composition obtained in Comparative Example 2 was mixed with 0.3 part of 8% cobalt octenoate as an accelerator, and mixed uniformly. Further, a radical curing agent (“328E”, A resin composition prepared by adding 1 part of an organic peroxide (manufactured by Yakuzo Akzo Co., Ltd.) and mixing the resulting mixture on a 350 mm × 350 mm glass plate subjected to a release treatment, is made of carbon fiber cloth (“Pyrofil TR3110MS”, Mitsubishi Rayon). (Carbon fiber for vinyl ester resin, manufactured by the company) by a hand lay-up molding method (8 ply) so that the volume content of carbon fiber is 50% and cured at room temperature (25 ° C.) for 12 hours. Then, it was further post-cured at 60 ° C. for 3 hours, and the compression strength and compression modulus were measured and evaluated. The results are shown in Table 3 as Comparative Example 2-FRP. Comparative Example 2-FRP had a lower strength value compared to Example 3-FRP and Example 4-FRP.

(Comparative Example 3)
In an appropriately sized container, 160 parts of alicyclic epoxy resin YX8000 (manufactured by Japan Epoxy Resin), 140 parts of alicyclic acid anhydride Ricacid MH-700G (manufactured by Nippon Nippon Chemical Co., Ltd.), curing catalyst Nissan Cation 2.4 parts of M2-100R (manufactured by NOF Corporation) was added and mixed to obtain an epoxy resin mixture.
Mold obtained by applying a release agent to two glass plates of 30 cm × 30 cm size, sandwiching a synthetic rubber tube between the glass plates, and using a spacer so that the gap is 3 mm. The casting plate was not cured at 80 ° C./3 hours, so that the casting temperature was gradually increased in the order of 100 ° C./2 hours and 120 ° C./5 hours to prepare a cast plate.
Instead of the casting plate obtained in Example 1, the mechanical properties and the heat distortion temperature were measured in the same manner as in Example 1 except that the casting plate obtained in Comparative Example 3 was used. Formability and punching shear were evaluated. The results are shown in Table 2.

(Comparative Example 4)
Polyurethane (VI) obtained in Synthesis Example 8 was diluted with a styrene monomer so that the non-volatile component would be 70% to obtain a radical polymerizable resin composition.
Except for using the obtained radical polymerizable resin composition, a casting plate was produced in the same manner as in Example 1, and the mechanical properties and thermal deformation temperature of the resulting casting plate were measured. Punching shear was evaluated. The results are shown in Table 2.

(Comparative Example 5)
The polyurethane (VII) obtained in Synthesis Example 9 was diluted with a styrene monomer so that the non-volatile component was 65% to obtain a radical polymerizable resin composition.
Except for using the obtained radical polymerizable resin composition, a casting plate was produced in the same manner as in Example 1, and the mechanical properties and thermal deformation temperature of the resulting casting plate were measured. Punching shear was evaluated. The results are shown in Table 2.

(Comparative Example 6)
46 parts of the unsaturated polyester obtained in Synthesis Example 6, 14 parts of the polyurethane (III) obtained in Synthesis Example 3 and 40 parts of styrene monomer were mixed to obtain a uniform solution to obtain a radical polymerizable resin composition.
Except for using the obtained radical polymerizable resin composition, a casting plate was produced in the same manner as in Example 1, and the mechanical properties and thermal deformation temperature of the resulting casting plate were measured. Punching shear was evaluated. The results are shown in Table 2.

(Cast plate production method)
The casting plates in Examples 1 to 5 and Comparative Examples 1, 2, 4 to 6 were produced as follows.
That is, Examples 1 to 5 were applied to a mold in which a release agent was applied to two glass plates of 30 cm × 30 cm in size, a synthetic rubber tube was sandwiched between the glass plates, and a gap was adjusted to 3 mm using a spacer. And 100 parts of the radical polymerizable resin composition obtained in Comparative Examples 1, 2, 4 to 6 was mixed with 0.3 parts of 8% cobalt octenoate as an accelerator and mixed uniformly, and further a radical curing agent. (“328E”, manufactured by Kayaku Akzo Co., Ltd., organic peroxide) is added and mixed with each resin composition. The resin composition is poured at room temperature for 1 day to cure redox, and after curing, the glass plate is dried. It was put into a machine, completely cured at 120 ° C. for 2 hours, and after cooling, the glass plate was removed to obtain a cast plate having a smooth thickness of 3 mm.

(Evaluation method 1. Viscosity)
The viscosity was measured according to JIS-K-6901 using the resin before curing in Examples 1-5 and Comparative Examples 1-6.

(Evaluation method 2. Mechanical properties)
The obtained cast plate was subjected to tensile measurement according to JIS-K-7113.

(Evaluation method 3. Thermal deformation temperature)
The heat distortion temperature of the obtained casting plate was measured according to JIS-K-7207.

(Evaluation method 4. Formability)
As evaluation of moldability, it evaluated by the hardening characteristic and resin viscosity of liquid resin. The case where the resin was curable at room temperature and the resin viscosity at room temperature was 50 dPa · s or less was evaluated as ○, and the other materials were evaluated as ×.

(Evaluation method 5. Punching shear)
A shear test by punching the obtained cast plate was evaluated according to JIS-K-7214. The case where a lot of cracks entered was evaluated as x, the case where a crack slightly occurred was evaluated as Δ, and the case where cracks did not occur was evaluated as ○.

(Evaluation method 6. Compression strength and compression modulus of FRP molded product)
The FRP laminates using carbon fibers molded according to the description in the above-described Examples and Comparative Examples were used, and the compression strength and compression modulus were measured according to JIS-K-7018.

As can be seen from the results in Tables 1 to 3, the casting plate obtained from the radical polymerizable resin composition of the present invention has an excellent balance of mechanical properties such as tensile strength and tensile elongation, heat resistance, and moldability. It was confirmed.

INDUSTRIAL APPLICABILITY The present invention can be used in a wide range of fields such as industrial material fields requiring high toughness and heat resistance, energy environment fields, vehicles / automotive fields, medical fields, electrical and electronic fields, mechanical fields, civil engineering and building fields.

Claims (12)

(Meth) acryloyl group-containing polyurethane (A) having the structure represented by the following general formula (I), (meth) acryloyl group-containing polyurethane (B) having the structure represented by the following general formula (II), and radical polymerization molding of the sexual unsaturated monomer (C) to contain and Lula radical polymerizable resin composition, fiber reinforcement and (D), characterized in that it is obtained by using an organic peroxide (E) Material .

(Y in general formula (I) represents an aliphatic cyclic structure-containing alkylene group, T represents an aliphatic cyclic structure-containing alkylene group or a chain alkylene group, and X represents a (meth) acryloyl group. (Indicating the atomic group to be included)

(Y ′ in the general formula (II) represents a structure having a polyether skeleton having an oxyalkylene unit having 2 or more carbon atoms, and T ′ represents an aromatic structure-containing compound or an aliphatic cyclic structure-containing alkylene. Represents a group or a chain alkylene group, and X represents an atomic group containing a (meth) acryloyl group. The molecular weight of the polyether skeleton portion of the (meth) acryloyl group-containing polyurethane (B) is 350 or more, and the (meth) acryloyl group with respect to 100 parts by mass of the (meth) acryloyl group-containing polyurethane (A). The molding material of Claim 1 which contains 10-100 mass parts of containing polyurethane (B). The (meth) acryloyl group-containing polyurethane (A) comprises an aliphatic cyclic structure-containing polyol (a1), an aliphatic cyclic structure-containing alkylene group or a chain alkylene group-containing polyisocyanate (a2), and an active hydrogen atom-containing The molding material of Claim 1 obtained by making (meth) acrylate (a3) react. The molding material according to claim 3, wherein the aliphatic cyclic structure-containing polyol (a1) is an aliphatic cyclic structure-containing polyol (a1-1) having a molecular weight of 100 to 300. The aliphatic cyclic structure-containing polyol (a1) is 1,4-cyclohexanedimethanol, and the aliphatic cyclic structure-containing alkylene group or chain alkylene group-containing polyisocyanate (a2) is isophorone diisocyanate, The molding material according to claim 3, which is dicyclohexylmethane diisocyanate or norbornene diisocyanate. The molding material of Claim 3 whose said active hydrogen atom containing (meth) acrylate (a3) is a hydroxyl-containing (meth) acrylate. The molding material according to any one of claims 1 to 6, wherein the fiber reinforcement (D) is glass fiber or carbon fiber. The molding according to any one of claims 1 to 6, wherein the fiber reinforcing material (D) is a carbon fiber, and the radical polymerizable unsaturated monomer (C) is a hydroxyl group-containing monomer. material. A molded article obtained by using the molding material according to claim 1 . A pipe comprising the molded product according to claim 9 . A container comprising the molded product according to claim 9 . A blade for wind power generation comprising the molded product according to claim 9 .

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