JP2003201340A - Unsaturated polyester and unsaturated polyester resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an unsaturated polyester which improves a working environment in a lining work because of the low volatility of contained monomers and is excellent in molding workability in FRP lamination because of the flexibility of a cured product, and to provide a method for producing the same. <P>SOLUTION: The method for producing the unsaturated polyester comprises reacting (A) a mixture of an unsaturated dicarboxylic acid with a monoester monocarboxylic acid prepared by reacting at least two of an acid imidoalcohol component, an alkyl alcohol component having at least one phenyl group, and dicyclopentadienyl- and/or oligocyclopentadienyl-residue containing components with (B) a polyhydric alcohol, (C) the unsaturated polycarboxylic acid and, optionally, (D) a saturated polycarboxylic acid. The unsaturated polyester is one containing at least two residues selected from the group consisting of acid imidoalcohol residues, phenyl-containing alkyl alcohol residues, and dicyclopentadienyl- and/or oligocyclopentadienyl residues as molecular terminal groups. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an unsaturated polyester, a method for producing the same, an unsaturated polyester resin (hereinafter referred to as “polyester resin”) in which a radical-polymerizable monomer and an additive are added to the unsaturated polyester, and the polyester. An unsaturated polyester resin composition (hereinafter referred to as "resin composition") obtained by adding fiber reinforcement, filler, etc. to a resin,
The present invention relates to a method of using the resin composition and a cured product obtained by using the resin composition. More specifically, the unsaturated polyester of the present invention has a low viscosity, and when used as a polyester resin, it reduces the compounding amount of the radical-polymerizable monomer (for example, styrene) to be added without deteriorating the physical properties of the molded product. As a result, it is possible to reduce the volatility of the radical-polymerizable monomer, and to obtain an unsaturated polyester resin with an improved working environment for lining work.
Among the polyester resins, it is possible to give a cured product having excellent flexibility and excellent durability (heat deterioration resistance, weather resistance, acid resistance, alkali resistance, water resistance).
P (Fiber Reinforced Plasti)
cs; fiber reinforced plastic), and provides an excellent resin composition as a waterproof resin and a mortar lining resin.

[0002]

2. Description of the Related Art Generally, a polyester resin or a resin composition is used as a base material of FRP (fiber reinforced plastic) used in, for example, construction materials, transportation equipment, industrial equipment, or casting, paint, adhesive, resin concrete. Widely used for resin mortar and decorative boards. This polyester resin is usually obtained by polycondensing an alcohol component composed of a polyhydric alcohol with an unsaturated polycarboxylic acid or an acid component composed of this and a saturated polycarboxylic acid or an aromatic polycarboxylic acid. It is a liquid resin obtained by mixing a radically polymerizable monomer, generally a styrene monomer, with a saturated polyester. In this case, the unsaturated polyester, polyhydric alcohols used in the production, unsaturated polyvalent carboxylic acids or saturated polycarboxylic acids and aromatic polyvalent carboxylic acids used in combination therewith the ratio of the type and blending amount By changing the composition, a suitable prepolymer is prepared, and a polyester resin or a resin composition which has physical properties suitable for the purpose of use or can be molded by a molding method suitable for the purpose of use is produced.

A typical polyester resin used for FRP contains 30% of styrene which is a radically polymerizable monomer.
About 55% by weight is contained. Therefore, the styrene contained in the polyester resin is volatilized during FRP molding in the open-mold molding method such as hand lay-up molding or spray-up molding, or during mixing and placing of resin concrete, which deteriorates the molding work environment. Often. In addition, with the enforcement of the PRTR (Environmental Pollutant Release and Transfer Registration System) Law, etc., the emission regulations of chemical substances are being tightened, and styrene contained in unsaturated polyester resins is also subject to this. In order to improve the working environment and to comply with regulations, it is required to suppress styrene volatilization and its measures.

There are roughly two methods for reducing the volatilization amount of styrene from the unsaturated polyester resin. The first method is a method in which an additive such as paraffin wax is added to the polyester resin to form a film of the additive on the surface of the liquid resin to suppress styrene volatilization from the resin surface. In this case, when the resin is left stationary, the additive forms a film on the resin surface, so the effect of suppressing styrene volatilization can be seen, but when performing hand lay-up molding or spray-up molding, or mixing resin concrete. -In the case of casting, the film formation by the additive is insufficient due to stirring and mixing, and the effect of suppressing volatilization of styrene is significantly reduced.

Further, additives such as paraffin wax added to the polyester resin are separated from the surface of the polyester resin while the polyester resin is stored and stored, and the effect of suppressing styrene volatilization is observed when the polyester resin is actually used for molding. Sometimes it can't be done. Further, it may be affected by the working temperature used, and the additive may not bleed onto the surface of the polyester resin, resulting in insufficient film formation on the surface. On the other hand, in the case of using polyester resin as an adhesive, or in the step of forming FRP in the FRP molding operation and then forming FRP on it and then adhering it (secondary adhesion), the above paraffin wax-based addition When the agent is added to the polyester resin,
It is unavoidable that the performance of the polyester resin as an adhesive is deteriorated.

The second method of reducing styrene volatilization is to lower the molecular weight of the unsaturated polyester to lower its viscosity,
In this method, the amount of radically polymerizable monomer (styrene) used for adjusting the viscosity of the polyester resin is kept low, and the amount of volatilization thereof is reduced. As a method for lowering the molecular weight, a method of controlling the reaction to suppress the molecular weight to a low level is disclosed in JP-A-53-9.
No. 2888 and JP-A-54-159492, a method of suppressing the molecular weight by modifying the terminal of the molecule by modification with dicyclopentadiene, and JP-A-52-3.
A monoalcohol as described in No. 686 or an acid imide alcohol obtained from a primary amino alcohol and a polybasic acid anhydride is used to block the molecular end.
There is a method to keep the molecular weight low. The primary amino alcohol of the acid imide alcohol is not particularly limited, and examples thereof include monomethylamino alcohol and 2-amino-
2-methyl-1-aminopropanol, tris (hydroxymethyl) aminomethane, 2-amino-2-ethyl-
1,3-propanediol or the like is used. This first
The polybasic acid anhydride that is reacted with a primary amino alcohol to form an acid imide alcohol is not particularly limited, and trimellitic anhydride, pyromellitic anhydride, benzophenone-
2,3,2 ', 3'-tetracarboxylic dianhydride, 3,
3 ′, 4,4′-diphenyltetracarboxylic dianhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhymic acid anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, Fumaric anhydride or the like is used. According to these methods, since the unsaturated polyester has a low molecular weight and a low viscosity, the absolute amount of styrene to be blended with the polyester resin is 3
Since it can be reduced to about 0% by weight, a stable styrene volatilization suppressing effect does not occur without causing instability of the styrene volatilization suppressing effect and a decrease in secondary adhesiveness as in the case of using a paraffin wax-based additive. Is obtained.

However, when simply lowering the molecular weight of the unsaturated polyester, the cured product obtained from the polyester resin having a lower molecular weight not only has lower mechanical properties such as strength and elongation but also further unsaturated. Since the hydrophilic terminal groups (hydroxyl group and carboxyl group) of the polyester increase, there is a problem that the water resistance of the cured product is greatly reduced. Further, in the case of a dicyclopentadiene-modified polyester resin whose molecule end is blocked by using a dicyclopentadienyl and / or oligocyclopentadienyl residue, workability during FRP molding is significantly reduced. In particular, there is a case where the compatibility with a glass fiber mat or a roving cloth, which is a fiber reinforcing material used for FRP molding, is deteriorated and the defibration property of the glass fiber mat (defibration due to dissolution of the binder of the glass fiber mat) is lost. There is a risk that the workability of molding will be significantly deteriorated. Further, this dicyclopentadiene-modified polyester resin is often problematic because its chemical structure and mechanical properties such as strength and elongation of a cured product obtained by lowering the molecular weight are often lowered.

On the other hand, in the case of a monoalcohol-blocked unsaturated polyester, a low boiling point having a small number of carbon atoms (for example, a boiling point of 100) is used.
When a monoalcohol of (° C. or lower) is used, it is difficult to complete the reaction because the alcohol flows out together with the produced water during the esterification reaction. On the other hand, when using a monoalcohol with a large number of carbon atoms and a high boiling point,
Esterification is easy, but the workability of the resin is significantly reduced. In particular, the compatibility with glass fiber mats and roving cloths used for FRP molding often deteriorates, and the defibration property of glass fiber mats is often lost, greatly deteriorating the molding workability. Further, the mechanical properties of the cured product may be deteriorated, the water resistance may be significantly reduced, and the dryness of the surface of the glass fiber reinforced cured product may be deteriorated, which often causes a problem. In the case of an end-capped unsaturated polyester with an acid imide alcohol residue, if the ratio shown at the molecular end is excessive, for example, more than 60%, the compatibility with the polymerizable monomer decreases, impairing viscosity reduction, and leaving the amino group remaining. The group may cause a decrease in water resistance.

[0009] In recent years, for waterproofing and anticorrosive construction of floors such as rooftops, balconies, parking lots, and factories, F has taken advantage of FRP's moldability, water resistance, mechanical characteristics (strength, etc.).
RP waterproofing has come to be used. In the FRP waterproofing structure, a primer is applied in advance in order to improve the adhesiveness between the resin and the base. As the primer material, a one-pack type moisture-curable urethane primer or the like is generally used. Then, using a polyester resin and a fiber reinforcement (such as a glass fiber mat), the resin is cured by lining to form an FRP waterproof layer. Finally, a topcoat resin is applied and cured as a finishing material.

As the polyester resin for FRP waterproofing and mortar lining, a soft unsaturated polyester is used in consideration of the adhesion to the substrate, the conformability to the substrate, and the relaxation of distortion of curing shrinkage. What is soft unsaturated polyester?
As described in the FRP waterproof construction guideline (draft), the resin cured product has a tensile strength of 10 MPa or more and a tensile elongation of 25% or more. This resin is used for FRP waterproofing and mortar lining. Is said to be preferable. Patent No. 25708898 and Patent No. 3131947
Unsaturated carboxylic acid as an unsaturated polyester component, isophthalic acid and terephthalic acid as a saturated carboxylic acid component, and diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol as a glycol component are used as essential components in a soft resin. Unsaturated polyester resins are shown and the effectiveness of using the above resins for FRP waterproofing is shown.

In the above patents and the like, by devising the formulation of unsaturated polyester for FRP waterproofing, the cured product is finished to be a soft and durable polyester resin, but the characteristics shown in them are cured. It relates to the initial properties of the product, and regarding durability, it relates only to fatigue properties, which are mechanical properties. These fatigue characteristics are also important factors for evaluating durability, but in actual use, the factors for evaluating chemical degradation are also more important factors for durability.

In particular, the type in which diethylene glycol, triethylene glycol, adipic acid, etc. are frequently used as the raw material of the unsaturated polyester has poor water resistance / alkali resistance, etc., and the flexibility of the cured product may decrease as the performance decreases. In addition, the type in which a large amount of diethylene glycol, triethylene glycol, polyethylene glycol, etc. is used as a raw material, when a cobalt-based accelerator generally used for FRP waterproof resin is used, it is likely to cause heat deterioration and decrease in flexibility. Sometimes. In the above resin, water resistance, which is the chemical durability of the waterproof material, chemical resistance,
It does not consider deterioration resistance such as heat deterioration resistance, acid resistance, alkali resistance, and weather resistance.

Therefore, when the resin containing these is used for a long time as a waterproof material for roofs, balconies, parking lots, aquariums, etc., which is its application, the water resistance of the soft polyester resin, which is a component of the waterproof material, is increased. Resistance, chemical resistance, heat resistance,
Deterioration of resin due to deterioration of weather resistance,
It becomes difficult to continue to exhibit its performance, and the FRP waterproof material often causes a problem of performance degradation such as cracking and swelling. On the other hand, in recent years, a ten year guarantee of the structural performance of a new house is obligatory, and a waterproof material is required to have a performance guarantee of ten years or more. Under such an environment, it is often the case that the present soft unsaturated polyester resin cannot sufficiently satisfy these required performances.

Therefore, from users of unsaturated polyester resins, FRP waterproofing contractors, and mortar lining contractors, for example, radical polymerization can be performed by using a low styrene content unsaturated polyester resin with a reduced content of radical polymerizable monomers. Unsaturated polyester resin that retains the effect of suppressing volatilization of organic monomer (low styrene volatility) and is excellent in molding workability of FRP laminate, and that does not cause deterioration of physical properties of the cured product The development of soft unsaturated polyester resins and cured linings that are durable and capable of improving the working environment and reducing odor is required.
With the tightening of regulations, the unsaturated polyester resin having the above-mentioned properties has been desired to be developed by a molder who is a user of the unsaturated polyester resin composition.

[0015]

DISCLOSURE OF THE INVENTION The present invention reduces the content of the radical-polymerizable monomer blended in the polyester resin to suppress the volatility of the radical-polymerizable monomer to a low level,
FRP molding work and resin concrete molding work, the work environment at the time of lining work can be improved and the odor can be reduced, and the obtained resin cured product has excellent flexibility and can give a resin cured product having excellent durability, An unsaturated polyester used for a resin composition which has excellent workability in FRP lamination and does not cause deterioration of physical properties of a cured product even if the molecular chain is short, a method for producing the same, and further durability by using the polyester resin. Excellent FRP waterproof material, resin mortar lining, and FRP with excellent surface smoothness
It is an object of the present invention to provide a molded product, a resin concrete molded product having low shrinkage, and a method for producing the resin concrete.

[0016]

The present invention provides [1] an acid imide alcohol residue, an alkyl alcohol residue having one or more phenyl groups, and a dicyclopentadienyl and / or oligocyclopenta group as a molecular end group. Unsaturated polyesters containing at least two residues from the group consisting of dienyl residues, [2] acid imide alcohol residues, alkyl alcohol residues having one or more phenyl groups, and dicyclo The above-mentioned [1], which contains at least two residues in the group consisting of pentadienyl and / or oligocyclopentadienyl residues, and the most residues are 90 mol% or less of the molecular end groups. Unsaturated polyester,

[3] An unsaturated polyester containing at least (a) an acid imide alcohol residue, an alkyl alcohol residue having one or more phenyl groups as a molecular end group, (b) an acid imide alcohol residue, and dicyclohexyl. Unsaturated polyester containing pentadienyl and / or oligocyclopentadienyl residues, or (c) alkyl alcohol residue having one or more phenyl groups, dicyclopentadienyl and / or oligocyclopentadienyl residues In the unsaturated polyester containing two residues of a group, the unsaturated polyester according to the above [1] or [2], wherein these residues are ester-bonded with a carboxyl group at the molecular end, [4] The central part of the molecular chain is polypropylene glycol and / or bisphenol A, bis At least one polyhydric alcohol residue selected from propylene oxide adducts of the group consisting of phenol AD, bisphenol F and bisphenol S, or a polyester chain comprising the polyhydric alcohol residue and a polycarboxylic acid residue. And at least two residues of the group consisting of an acid imide alcohol residue, an alkyl alcohol residue having one or more phenyl groups and a dicyclopentadienyl and / or oligocyclopentadienyl residue as a terminal group of the molecule. Bonded groups,
Number average molecular weight in terms of polystyrene is 600 to 3000,
The unsaturated polyester according to any one of [1] to [3] above, which has a weight average molecular weight of 800 to 5000.

[5] The polyhydric alcohol component is polypropylene glycol having a molecular weight of 190 to 2000 and /
Or bisphenol A having a molecular weight of 650 to 2000,
The soft unsaturated polyester according to any one of the above [1] to [4], which is at least one selected from the group consisting of propylene oxide adducts of bisphenols consisting of bisphenol AD, bisphenol F and bisphenol S, [6 ] Unsaturated polyester (UP
Unsaturated polycarboxylic acid monoester residue at the end of E) [an unsaturated dicarboxylic acid having one carboxyl group and an acid imide alcohol residue, an alkyl alcohol residue having one or more phenyl groups and a dicyclopentadienyl residue] And / or monoester monocarboxylic acid residue in which at least two of oligocyclopentadienyl residues are half-ester-bonded (MMC residue) (F
F), FF = [(number of moles of MMC residue) / (number of moles of UPE) ×
2)] × 100 (however, the number of moles of MMC residue = the number of moles of monoester monocarboxylic acid, and the number of moles of UPE = the total weight of UPE / the number average molecular weight). The unsaturated polyester according to the above [1], wherein the occupancy of the unsaturated polycarboxylic acid monoester residue in the polyester terminal is 60% or more.

[7] (A) acid imide alcohol component,
At least two monoalcohol components selected from the group consisting of an alkyl alcohol component having one or more phenyl groups and a dicyclopentadienyl and / or oligocyclopentadienyl residue-containing component, (B) a polyhydric alcohol component, and ( C) unsaturated polycarboxylic acid component or a method for producing an unsaturated polyester, characterized by reacting (D) saturated polycarboxylic acid component with them, [8]
At least two monoalcohol components selected from the group consisting of unsaturated dicarboxylic acids and acid imide alcohol components, alkyl alcohol components having one or more phenyl groups and dicyclopentadienyl and / or oligocyclopentadienyl residue-containing components. The method for producing an unsaturated polyester according to the above [7], which uses a reacted monoester monocarboxylic acid mixture,

[9] (A) acid imide alcohol component,
At least two monoalcohol components selected from the group consisting of an alkyl alcohol component having one or more phenyl groups and a dicyclopentadienyl and / or oligocyclopentadienyl residue-containing component, and (B) polypropylene glycol, bisphenol A, Bisphenol AD,
A polyhydric alcohol component containing at least 50 parts by weight per 100 parts by weight of a polyhydric alcohol component, and at least one selected from the propylene oxide adducts of the group consisting of bisphenol F and bisphenol S; Esterification reaction with at least one unsaturated carboxylic acid component selected from a carboxylic acid and a reactive derivative thereof, or at the same time with these, (D) saturated polycarboxylic acid, aromatic polycarboxylic acid An esterification reaction is carried out with a saturated polycarboxylic acid component which is at least one selected from an acid and its reactive derivative, and an acid imide alcohol residue and an alkyl alcohol residue having one or more phenyl groups at the end groups. And at least one of the group consisting of dicyclopentadienyl and / or oligocyclopentadienyl residues One of the residues bound to a number average molecular weight in terms of polystyrene 600 to 3000, a method of manufacturing a flexible unsaturated polyester, characterized in that the weight average molecular weight to produce a polyester of 800 to 5000, [1
0] The ratio of the unsaturated polycarboxylic acid (C) to the saturated polycarboxylic acid (D) is set to a ratio of (D) / (C) = 0 to 4.00 in the above [7] to [9]. A method for producing a soft unsaturated polyester according to any one of the following:

[11] It is characterized in that 5 to 55 parts by weight of a copolymerizable radically polymerizable monomer is mixed with 100 parts by weight of the unsaturated polyester described in any of [1] to [6]. Unsaturated polyester resin, [1
2] The unsaturated polyester resin 1 according to the above [11]
FRP waterproof material in which 15 to 80 parts by weight of the fiber reinforcement is mixed with 00 parts by weight, [13] to the pretreated base,
[14] A method for applying an FRP waterproof material, characterized by applying and curing the FRP waterproof material according to [12] above.
The unsaturated polyester resin according to the above [11], and a filler and / or an aggregate of 100 to 100 parts by weight of the resin.
Resin mortar lining material mixed with 500 parts by weight,

[15] A method for applying a cured resin mortar lining, which comprises applying the resin mortar lining material according to the above [14] to a pretreated base and curing it, [16] above [11] 100 parts by weight of the unsaturated polyester resin described in [4], and a composition for resin concrete in which 300 to 1300 parts by weight of a filler / aggregate are mixed, and [17] 100 parts by weight of the unsaturated polyester resin described in [11] above. On the other hand, the above object was achieved by developing a resin concrete molded product obtained by mixing 300 to 1300 parts by weight of a curing agent and a filler / aggregate and curing the mixture.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that the molecular terminal group of unsaturated polyester has an alkyl imide alcohol residue or an alkyl group having one or more phenyl groups. The unsaturated polyester containing at least two residues from the group consisting of alcohol residues and dicyclopentadienyl and / or oligocyclopentadienyl residues is characterized by containing two or more of these residues. Compared with the above-mentioned one having only one functional group, it has an advantage that it has lower viscosity and does not deteriorate other physical properties, and that it is easy to synthesize. For this reason, the amount of radically polymerizable monomer required for viscosity adjustment is not particularly required, and it has the characteristic that it can be minimized for cross-linking, reducing the volatilization amount of the monomer and working under open conditions. The environmental pollution at the time can be greatly reduced.

Among the above unsaturated polyesters, the alcohol component consisting of polyhydric alcohol has a molecular weight of 190
To 2,000 polypropylene glycol and / or a polyhydric alcohol consisting of bisphenol A, bisphenol AD, bisphenol F and bisphenol S having a molecular weight of 650 to 2000 (bisphenol A, bisphenol AD, bisphenol F and bisphenol S are collectively referred to as "bisphenol-based polyphenol Alcohol "
Say. It has been found that when an esterification reaction is carried out using an alcohol component containing a polyhydric alcohol component consisting of at least one of the propylene oxide adducts in 1), a soft polyester resin is produced without deteriorating other performances. The present invention has been completed based on these findings.

The present invention will be described in more detail below. In the unsaturated polyester used in the unsaturated polyester of the present invention, at least the component (A) may be an alcohol component having at least one acid imide bond. The alcohol having an acid imide bond in the molecule is a saturated or unsaturated polyvalent carboxylic acid anhydride or aromatic polyvalent carboxylic acid anhydride, preferably a radically polymerizable unsaturated polyvalent carboxylic acid and an amino group. It can be produced by reacting one or more alkyl alcohols to synthesize an acid imide. Examples of saturated or unsaturated polycarboxylic acid anhydrides or aromatic polycarboxylic acid anhydrides include maleic anhydride, itaconic anhydride, chloromaleic anhydride, phthalic anhydride, succinic anhydride, and tetrahydrophthalic anhydride. , Hexahydrophthalic anhydride, chlorendic anhydride, endomethylenetetrahydrophthalic anhydride,
Commercially available polycarboxylic acid anhydrides such as tetrabromophthalic anhydride, trimellitic anhydride, and pyromellitic dianhydride can be mentioned.

Examples of aminoalkyl alcohols having one or more amino groups used as raw materials for acid imide alcohols include 2-aminoethanol, aminopropanol, aminoisopropanol, aminobutanol, aminopentanol, diaminopropanol, aminobenzyl alcohol. Examples thereof include commercially available amino compounds.

The reaction ratio of the acid anhydride component and the alkyl alcohol component having one or more amino groups is such that the acid anhydride / amino group (-NH ₂ ) is 1.0 to 1.05 equivalent ratio. In the acid imidization reaction, first, a polyvalent carboxylic acid anhydride and an alkyl alcohol having at least one amino group are treated with 0
Amidation is carried out by adding an acid anhydride to the amino group while paying attention to the exotherm between ℃ and 100 ℃. Continuously 120 ° C
To 180 ° C. for dehydration reaction to form acid imidization. When the carboxylic acid anhydride component and the amino alcohol component are imidized, an acid imide alcohol is obtained, but depending on the combination, it may crystallize and impair the stability of the liquid resin. It is preferable to use.

In the unsaturated polyester of the present invention,
There is a monoalcohol component containing an alkyl alcohol having one or more phenyl groups as the component (A). As the monoalkyl alcohol having at least one phenyl group, an alkyl group having 1 to 4 carbon atoms is used.
If one having 4 or more carbon atoms is used, water resistance may be deteriorated. Examples of these monoalcohols include commercially available phenylalkyl alcohols such as benzyl alcohol, phenylethanol, phenylpropanol and phenylbutanol. In particular, benzyl alcohol having a small number of carbon atoms in the alkyl group is preferable in order to improve workability during FRP lamination work and to prevent deterioration in water resistance.

In the unsaturated polyester of the present invention, a dicyclopentadiene and / or oligocyclopentadiene residue is introduced at the molecular end. It uses a precursor of dicyclopentadiene and / or oligocyclopentadiene residues and unsaturated dicyclopentadiene and / or oligocyclopentadiene residues with acid imide alcohol residues and / or alcohol residues with phenyl groups. By introducing at the molecular end of the polyester, the viscosity of the unsaturated polyester is reduced, and even if the amount of the radically polymerizable monomer is reduced, the volatilization amount of the monomer can be reduced without inviting a decrease in water resistance or physical properties of the cured product, and F
It is intended to obtain an unsaturated polyester capable of preventing a decrease in workability during RP molding work.

Specifically, the dicyclopentadienyl residue and the oligodicyclopentadienyl structural unit are all derived from the starting material dicyclopentadiene,
As such it is the dimerization product of cyclopentadiene. Cyclopentadiene spontaneously dimerizes at room temperature to dicyclopentadiene. Temperature above 100 ° C,
Cyclopentadiene reacts itself to the oligodicyclopentadiene via dicyclopentadiene as an intermediate step, preferably at 170-300 ° C. and under pressure, by the mechanism of the Diels-Alder reaction.

In this case, dicyclopentadiene and / or
Alternatively, as the oligocyclopentadiene residue precursor, dicyclopentadiene malate and / or half ester of dicyclopentadiene fumarate (R ester:
It is possible to lower the viscosity of the resulting unsaturated polyester and increase the degree of cross-linking at the molecular ends by using (acidic content), which not only reduces the amount of radically polymerizable monomers, but also the water resistance and surface of the cured product. It is possible to prevent deterioration of drying property.

The dicyclopentadiene and / or oligocyclopentadiene maleate and the dicyclopentadiene and / or oligocyclopentadiene fumarate are, for example, maleic anhydride and water at 50 ° C. to 10 ° C.
It can be synthesized by reacting at 0 ° C. to synthesize maleic acid, further adding dicyclopentadiene and / or oligocyclopentadiene, and reacting at 120 ° C. to 140 ° C. Even when maleic acid is used, a part of it undergoes trans rearrangement to form a fumarate ester, and a mixed ester of maleate and fumarate is synthesized. In the unsaturated polyester of the present invention, the component synthesized by such a procedure can be used as it is as a raw material. In this case, the unsaturated polyester of the present invention can also be synthesized by adding a polyhydric alcohol component, an unsaturated polycarboxylic acid and a saturated polycarboxylic acid component to the reaction system subsequent to the above synthesis.

Further, as the component (A) (monoalcohol), an acid imide alcohol residue, an alkyl alcohol residue having one or more phenyl groups, and a raw material alcohol for a dicyclopentadiene and / or oligocyclopentadiene residue are used in combination. As the monoalcohol that can be used, a monovalent alkyl alcohol having a boiling point of 100 ° C. or higher can be used. Examples thereof include aliphatic ones such as hexanol, heptanol, octanol, and 2ethylhexanol, and cyclohexanol, tetrahydrofurfuryl alcohol, methylcyclohexynylmethanol, phenoxymethyl alcohol, phenoxyethyl alcohol, phenoxypropyl alcohol, and other cyclic fatty acids. Examples include group-based and monoalcohols having an ether bond. From these, it is preferable to select and use the kind and the amount used that do not affect the durability according to the purpose.
Only one kind may be used, or two or more kinds may be used in combination.

The terminal group of the molecule has an acid imide alcohol residue,
An unsaturated polyester having at least two residues in the group consisting of an alkyl alcohol residue having one or more phenyl groups and a dicyclopentadiene residue and / or an oligocyclopentadiene residue, resulting in a low viscosity unsaturated compound. It is possible to use polyester, and as a result, it is possible to obtain an unsaturated polyester resin that can reduce the content of radically polymerizable monomers, and the obtained unsaturated polyester resin has durability, water resistance, chemical resistance, etc. It can be an excellent cured product. Unsaturated polyester (UP
Unsaturated polycarboxylic acid monoester residue at the end of E) [an unsaturated dicarboxylic acid having one carboxyl group and an acid imide alcohol residue, an alkyl alcohol residue having one or more phenyl groups and a dicyclopentadienyl residue] And / or monoester monocarboxylic acid residue in which at least two of oligocyclopentadienyl residues are half-ester-bonded (MMC residue) (F
F) is calculated by the following formula. FF = [(number of MMC residue moles) / (number of UPE moles x
2)] × 100 (however, the number of moles of MMC residue = the number of moles of monoester monocarboxylic acid, and the number of moles of UPE = total weight of UPE / number average molecular weight). If it contains a carboxylic acid residue, it is effective, but the occupancy rate of the unsaturated polyvalent carboxylic acid monoester residue in the unsaturated polyester terminal (FF)
Is preferably 60% or more.

Since it is impossible to measure all of the molecular end groups, the acid imide alcohol residue, the alkyl alcohol residue having one or more phenyl groups, the dicyclopentadiene and the / Or the ratio of oligocyclopentadiene residues is defined. In this case, when the above-mentioned residues are two types,
The large amount of the residues is 90 mol% or less of the whole molecular end group, and preferably the large amount of the two kinds of the above residues is 60 mol% or less. If the lesser of the two types of residues is less than 10 mol%, the effect is not exhibited. About 50% or more when the alkyl alcohol residue having one or more phenyl groups is used alone for the end capping of the unsaturated polyester, and about 55% when only the dicyclopentadiene and / or oligocyclopentadiene residue is used. % Or more, about 60 in the case of end-capping with an acid imide alcohol residue alone.
If the amount exceeds 50%, the compatibility with the polymerizable monomer decreases, the viscosity reduction is impaired, and the amino group residue may reduce the water resistance. However, when two or more of these residues are used in combination, even if the total ratio of the monoester leaving group occupying the terminal exceeds the above upper limit, these problems do not occur and the properties can be maintained.

Examples of the polyhydric alcohol component (B) used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 2-methyl-1, 3-propanediol, 1,
2-butanediol, 1,3-butanediol, 1,4
-Butanediol, 2,3-butanediol, 1,5-
Pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-
1,3-propanediol (neopentyl glycol), methyloctanediol, nonanediol, 1,
4-cyclohexanediol, 1,4-cyclohexanedimethanol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, polyethylene glycol, polytrimethylene ether glycol, polytetramethylene ether glycol, polycaprolactone diol, poly Examples include commercially available polyhydric alcohols such as valerolactone diol.

Particularly when a soft cured product is intended,
As the component (B) (polyhydric alcohol), a polyhydric alcohol component containing at least one of polypropylene glycol and / or propylene oxide adduct of bisphenol-based polyhydric alcohol is used. Polypropylene glycol is preferably poly (1,2-oxypropylene diol) having a molecular weight of 190 to 2000. If the molecular weight is smaller than these ranges, the flexibility of the cured product may not be sufficiently obtained and the water resistance may be reduced. When the molecular weight is larger than these ranges, flexibility is obtained but further effects cannot be obtained, and it is rather difficult to esterify and incorporate it in the molecular skeleton.

The propylene oxide adduct of bisphenol type polyhydric alcohol has a molecular weight of 650 to 20.
A propylene oxide adduct of 00 bisphenol A, bisphenol AD, bisphenol F and bisphenol S is used. If the one having a molecular weight smaller than these ranges is used, the flexibility of the cured product cannot be sufficiently obtained, and if the molecular weight is larger than these ranges, the flexibility is obtained, but there is no further effect, and rather esterification leads to a molecular skeleton. It becomes difficult to install.

When a soft cured product is intended, the propylene oxide adduct of polypropylene glycol and / or bisphenol type polyhydric alcohol is 50 parts by weight or more, preferably 75 parts by weight or more per 100 parts by weight of the polyhydric alcohol component. More preferably, the total amount is polypropylene glycol or bisphenol-based polyhydric alcohol. If the content is less than 50 parts by weight, the cured product of the unsaturated polyester resin may not have sufficient flexibility or may have reduced water resistance. Of these polyhydric alcohols, only one kind may be used, or two or more kinds may be used in combination.

The component (B) (polyhydric alcohol) is polypropylene glycol and / or bisphenol A,
Other than the propylene oxide adduct of bisphenol AD, bisphenol F and bisphenol S, other polyhydric alcohol components that can be used are used. Examples of other alcohol components include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol,
Dipropylene glycol, tripropylene glycol,
1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5- Pentanediol, 3-methyl-
1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), methyloctanediol, nonanediol, 1,4-cyclohexanediol, 1,
4-cyclohexanedimethanol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, polyethylene glycol, polytrimethylene ether glycol, polytetramethylene ether glycol, polycaprolactone diol, polyvalerolactone diol, bisphenol A and Examples include commercially available polyhydric alcohols such as ethylene oxide adducts of F and S.

Further, the molecular weight is less than 190 or 2000
Other than the above polypropylene glycol, a molecular weight of less than 650 or 2,000 other than the above bisphenol A and propylene oxide adducts of AD, F and S, and 2,2-di [4-hydroxycyclohexyl]
Examples also include polyhydric alcohols containing a hydrogenated bisphenol skeleton such as propane (hydrogenated bisphenol A). In addition, PET (polyethylene terephthalate),
It is also possible to use PBT (polybutylene terephthalate), PEN (polyethylene naphthalate) or the like that has been subjected to alcoholysis with glycol. It is preferable that these alcohol components are used in a combination and an amount range that does not impair the flexibility and durability of the obtained resin.

In order not to reduce the surface smoothness of the FRP molded product or to reduce the molding workability and shrinkage of the resin concrete, the polyhydric alcohol component containing the bisphenol skeleton and / or the hydrogenated bisphenol skeleton is entirely It is used in a composition containing 20 parts by weight or more with respect to 100 parts by weight of the alcohol component. By using a polyhydric alcohol component containing a bisphenol skeleton and / or a hydrogenated bisphenol skeleton in this ratio or more,
The low shrinkage effect is enhanced, and the shrinkage rate of the resulting resin can be further reduced.

Particularly, in order not to reduce the molding workability and shrinkage of resin concrete, propylene glycol, 2-methyl-1,3-propanediol, 1,2-
Butanediol, 2,3-butanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), and ethylene glycol are preferably selected and used.

In the unsaturated polyester of the present invention,
As the acid component of the component (C) (unsaturated polycarboxylic acid),
An acid component consisting of at least one selected from unsaturated polycarboxylic acids and / or reactive derivatives thereof is used as an essential component. Examples of the unsaturated polycarboxylic acid as the component (C) include maleic acid, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid and the like. Examples of these reactive derivatives include acid anhydrides such as maleic anhydride, itaconic anhydride and chloromaleic anhydride, and lower alkyl esters of the above unsaturated polycarboxylic acids. These unsaturated polycarboxylic acids and their reactive derivatives may be used alone or in combination of two or more, but in general, considering the balance of cost and performance, maleic anhydride, fumaric acid. Is used.

Further, the component (D) (saturated polycarboxylic acid) is to use an acid component comprising at least one selected from saturated aliphatic polycarboxylic acids, aromatic polycarboxylic acids and reactive derivatives thereof. You can also Examples of the saturated aliphatic polycarboxylic acid, the aromatic polycarboxylic acid and the reactive derivative thereof as the component (D) include succinic acid, adipic acid,
Saturated aliphatic polycarboxylic acids such as sebacic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid phthalic anhydride, and hexahydrophthalic acid (cyclohexanedicarboxylic acid) can be mentioned. Orthophthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid. , Aromatic polycarboxylic acids such as trimellitic acid and pyromellitic acid. Further examples include halogenated phthalic acid such as chlorendic acid (het acid) and tetrabromophthalic acid.

Examples of these reactive derivatives include succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride (cyclohexanedicarboxylic anhydride), chlorendic anhydride, and endomethylenetetrahydrophthalic anhydride. Acid anhydrides such as tetrabromophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, or saturated polycarboxylic acids and aromatic polycarboxylic acids such as dimethyl phthalate, diethyl phthalate, dimethyl isophthalate and dimethyl terephthalate. Lower alkyl ester and the like can be mentioned. These saturated polyvalent carboxylic acids, aromatic polyvalent carboxylic acids, and their reactive derivatives may be used alone or in combination of two or more. It is preferable that these acid components are used in a combination and in a range of the amount used so as not to impair the flexibility and durability of the obtained resin.

In the unsaturated polyester of the present invention, the alcohol component of the component (A) (monoalcohol) and the component (B) (polyhydric alcohol) and the acid component of the component (C) (unsaturated polycarboxylic acid) are used. Alternatively, it can be produced by condensation polymerization of the component (C) + the component (D) (saturated polycarboxylic acid). Although not specified in particular,
The alcohol component consisting of (A) + (B) is used in a ratio range of 0.90 to 1.20 equivalents to 1.0 equivalent of the acid component of the component (C) or the component (C) + (D), That is, the ratio of hydroxyl group / carboxyl group (OH / COOH) is 0.90 to 1.30, more preferably 1.0.
The esterification reaction (polycondensation) is carried out by using a ratio of 5 to 1.15.

In the present invention, although not particularly specified, the (A) component and the (B) alcohol component are
Usually, the hydroxyl equivalent ratio is (A) / (B) = 0.25 to 1.
00, preferably 0.3 to 1.00. Further, the component (C) and the component (D) are usually used in a molar ratio (D) / (C) = 0 to 4.00, preferably 0 to 2.
A combination of 100 is used.

In the present invention, the component (A) (monoalcohol), which is the residue at the molecular end, is previously reacted with the unsaturated polycarboxylic acid, and the component (A) of the unsaturated carboxylic acid is added to the molecular end. It is preferable that the monoalcohol half-ester residues are bound to each other and that unsaturated groups are present as close to both ends of the unsaturated polyester molecule as possible. By doing so, a cured product having good performance can be obtained even with a low molecular weight unsaturated polyester. On the other hand, when aiming at a soft cured product, an unsaturated polyester having as few unsaturated groups as possible in the central part of the molecular chain is preferable, so that the terminal part is preliminarily reacted with an unsaturated polycarboxylic acid to form a polyester. Unsaturated carboxylic acid is not used in the reaction at all, or its compounding ratio is reduced as much as possible, or long-chain polypropylene glycol etc. is used for the polyhydric alcohol component, so that the unsaturated bond in the central part of the molecular chain is It is preferable to minimize

In the unsaturated polyester of the present invention, R ¹ —OCOCR ⁴ ═CR ⁴ (CH ₂ ) mCO [OR ² O (COR ³ CO) _K ] _n —R ² OCO (CH ₂ ) is mainly used in the unsaturated polyester. mCR ⁴ = CR ⁴ COO-R ¹ ··· (1) [wherein R ¹ is an acid imide alcohol residue, an alkyl alcohol residue having one or more phenyl groups and dicyclopentadienyl and / or oligocyclo Shows at least two residues of the group consisting of pentadienyl residues,
R ² is a polyhydric alcohol residue or a polyester chain composed of a polyhydric alcohol residue and a polycarboxylic acid residue, R ³ is a polycarboxylic acid residue, and R ⁴ is other than an unsaturated bond of an unsaturated carboxylic acid. A side chain hydrocarbon group, k is 1 or 0, and m
Represents a number of 0 or 1 or more, and n represents a number of 0 or 1 or more. ], The polystyrene equivalent number average molecular weight is 6
The unsaturated polyester is a polyester having a weight average molecular weight of 00 to 3000 and a weight average molecular weight of 800 to 5000.

The molecular terminal group of such an unsaturated polyester comprises an acid imide alcohol residue, an alkyl alcohol residue having one or more phenyl groups and a dicyclopentadienyl and / or oligocyclopentadienyl residue. Polypropylene glycol having a molecular weight of 190 to 2,000, bisphenol A, bisphenol AD and bisphenol having a molecular weight of 650 to 2,000, which is composed of at least two residues in the group and further has a molecular skeleton as a polyhydric alcohol component in the central portion of the molecular chain. By adopting a structure having a polyhydric alcohol residue containing at least one propylene oxide adduct of F and bisphenol S, not only the content of the radically polymerizable monomer can be reduced but also a soft unsaturated polyester resin can be obtained. Done and got Quality Unsaturated polyester resins are flexible, durable, water-resistant, it can be a cured product excellent in chemical resistance.

The esterification reaction in the production of the unsaturated polyester of the present invention is carried out in a stream of an inert gas such as nitrogen at a temperature of 150 to 230 ° C. according to a conventional method, and it is carried out under pressure or under reduced pressure until a required step. Esterified. Also,
In the above esterification reaction, an esterification catalyst can be used if necessary. Examples of the catalyst include known catalysts such as manganese acetate, dibutyltin oxide, stannous oxalate, zinc acetate and cobalt acetate.

Next, the unsaturated polyester of the present invention is blended with a radical-polymerizable monomer copolymerizable with the polyester to obtain the soft unsaturated polyester resin of the present invention. Examples of the radical polymerizable monomer used in the unsaturated polyester resin of the present invention include styrene, α-methylstyrene, β-methylstyrene, vinyltoluene, chlorostyrene, dichlorostyrene, t-butylstyrene, divinylbenzene, vinylnaphthalene,
Ethyl vinyl ether, methyl vinyl ketone, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylonitrile, methacrylonitrile, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate,
Examples thereof include vinyl compounds such as ethylene glycol dimethacrylate and trimethylolpropane triacrylate, allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl succinate and triallyl cyanurate, and oligomers thereof. These radically polymerizable monomers may be used alone or in combination of two or more. Generally, styrene is preferably used.

The amount of the radically polymerizable monomer compounded in the unsaturated polyester resin of the present invention is a suitable range depending on the constitution of the unsaturated polyester such as molecular weight, kind of polyhydric alcohol, kind of carboxylic acid, purpose of use and construction method. different. Generally, in order to suppress volatilization of radically polymerizable monomers during FRP molding work, resin concrete molding work, and lining construction, it is possible to set the range of 5 to 55 parts by weight per 100 parts by weight of unsaturated polyester. And more preferably in the range of 5 to 35 parts by weight. Furthermore, in order to suppress the volatility of the radical polymerizable monomer, it is preferable to select and use a radical polymerizable monomer having a high boiling point.

If desired, a polymerization inhibitor may be added to the unsaturated polyester and the unsaturated polyester resin of the present invention. As the polymerization inhibitor, those conventionally used in unsaturated polyester resins, for example, hydroquinone, P-benzoquinone, methylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, catechol, t-butylcatechol, 2,6-diquinone. -T-butyl-4-methylphenol and the like can be mentioned.

To the unsaturated polyester resin of the present invention, 0.01 to 5 parts by weight of the silane compound represented by the general formula is added to 100 parts by weight of the unsaturated polyester resin. YRa-Si-Xb [wherein R is hydrogen, an alkyl group such as a methyl group, an ethyl group, a propyl group, a phenyl group, a vinyl group, or a methylene group, an ethylene group, a propylene group, a phenylene group,
An alkylene group such as a vinylene group is shown, and X is CH ₃ O.
-, CH ₃ CH ₂ O-, shows the Cl @ -, Y is hydrogen, an amino group (H ₂ N-), chlorine (Cl @ -), glycidyl ether _{{CH 2 (O) CHCH 2} O-}, methacrylate { C
_{H 2 = C (CH 3)} COO-}, thiol (HS-), isocyanate (OCN-) shows a further a + b = a 4 and, a is an integer from 0 3, b is from 1 4 Indicates an integer. ]

Examples of these silane compounds are tetramethoxysilane, tetraethoxysilane, trimethoxyphenylsilane, triethoxyphenylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, trimethoxyγ-aminopropylsilane, trimethoxyγ.
An alkoxysilane compound such as methacryloxypropylsilane, trimethoxyγ-glycidoxypropylsilane, trimethoxyγ-isocyanatopropylsilane,
Further, chlorosilane compounds such as trichloromethylsilane, trichlorovinylsilane and trichlorophenylsilane can be mentioned. You may use only one of these,
Also, two or more kinds may be used in combination with other materials.
By adding the silane compound, the adhesion between the resin and the aggregate in the case of producing the resin concrete is improved, and the strength is improved. If the addition amount is lower than this range, there is no effect, and if the addition amount is higher than this range, no further addition effect can be obtained.

The unsaturated polyester and the unsaturated polyester resin of the present invention can be easily cured by normal temperature curing or heat curing by adding a curing agent and a curing accelerator which are commonly used to ordinary unsaturated polyester resins. Examples of the curing agent include methyl ethyl ketone peroxide, acetylacetone peroxide, t-butyl peroctoate, t-butyl peroxybenzoate,
Benzoyl peroxide, dicumyl peroxide,
Organic peroxides such as cumene hydroperoxide may be mentioned. For FRP waterproofing, methyl ethyl ketone peroxide is generally preferred and used.

On the other hand, examples of the curing accelerator include cobalt naphthenate, cobalt octoate, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-P-toluidine, acetylacetone and ethyl acetoacetate. Examples thereof include esters. For FRP waterproofing, a cobalt-based accelerator such as cobalt naphthenate or cobalt octoate is generally preferably used in combination with methyl ethyl ketone peroxide which is a curing agent. If necessary, other accelerators are used in combination.

By using the unsaturated polyester resin of the present invention in combination with a fiber reinforcing material and molding and curing, a gel coat-coated FRP laminate having improved surface smoothness can be prepared. As the fiber reinforcing material used in combination, glass fibers, carbon fibers, polyester fibers, aramid fibers, organic or inorganic such as vinylon fibers, and
Mention may be made of synthetic or natural fiber reinforcements. Their shapes are chops, chopped strand mats, continuous strand mats, rovings, roving cloths, plain weaves, satin weaves, twill weaves, cloths, braids,
Three-dimensional fabrics, braids, etc. can be used. The amount of the fiber reinforcing material used is 100 parts by weight of the curable resin composition,
10 to 200 parts by weight.

Further, if necessary, a filler such as calcium carbonate or aluminum hydroxide, a thermoplastic resin such as polystyrene, polyvinyl acetate, polybutadiene, a styrene-vinyl acetate copolymer, and saturated polyester may be appropriately blended. it can. Furthermore, if necessary, various additives such as a thixotropic agent, a pigment, a release agent, an antioxidant, an ultraviolet absorber, an impregnating agent, an antifoaming agent, etc. may be added within a range that does not impair the object of the present invention. You can As a molding method for molding an FRP laminate having excellent surface smoothness, a hand lay-up molding method, a spray-up molding method, a filament winding molding method, or the like can be applied. Furthermore, as applications, surface smoothness of boats, ships, housing equipment (baths, septic tanks, water-related products, etc.), automobile vehicle parts, etc. is required.
Very suitable for RP laminated molded products.

By using the unsaturated polyester resin of the present invention in combination with a filler and an aggregate and curing the mixture,
It is possible to produce a resin concrete and a resin mortar cured product which are free from cracks, warpage, and deformation and have excellent physical properties. Examples of fillers used in combination include calcium carbonate, aluminum hydroxide, fly ash,
Barium sulfate, talc, kaolin, clay, glass powder, wood powder, and the like, further, glass microballoons, shirasu balloons, saran resin microballoons,
Examples thereof include hollow fillers such as acrylonitrile microballoons. Examples of aggregates include silica sand, crushed stone,
Typical aggregates such as gravel, synthetic aggregates synthesized from incinerated ash, lightweight aggregates, and the like are included. For mortar, those having a particle size of about 5 mm or less are preferable.
The blending amount of these fillers and aggregates is not particularly specified, but is 300 parts by weight to 1300 parts by weight with respect to 100 parts by weight of the curable resin composition.

Further, if necessary, an organic or inorganic fiber reinforcing material such as glass fiber, carbon fiber, polyester fiber, aramid fiber, vinylon fiber or steel fiber,
Thermoplastic resins such as polystyrene, polyvinyl acetate, and polybutadiene can be appropriately mixed. Further, depending on the required performance of resin concrete and resin mortar products, reinforcing materials such as reinforcing bars, FRP bars and wood can be used if necessary. Furthermore, if necessary, various additives such as a thixotropic agent, a pigment, a release agent, an antioxidant, an ultraviolet absorber, an impregnating agent, an antifoaming agent, etc. may be added within a range that does not impair the object of the present invention. You can

As a molding method of the resin concrete and the resin mortar cured product which can be produced by combining the curable resin composition of the present invention with the filler and the aggregate, a casting method, a compression molding method, a centrifugal molding method or the like is applied. You can Applications of the resin concrete and cured resin mortar obtained from the cured product of the curable resin composition of the present invention include pipe products, manholes, water collecting masses, water and sewer-related materials and information such as lids, and communication-related materials. Boxes are included.

The unsaturated polyester resin of the present invention is FR
P Additives such as antioxidants, UV absorbers, impregnants, defoamers, paraffin wax, and higher hydroxy fatty acid esters to improve workability and surface dryness for use in waterproofing and resin mortar linings. You may add a kind. Generally, the blending ratio of fiber reinforcement is
The amount of the fiber reinforcing material is 15 to 80 parts by weight with respect to 100 parts by weight of the unsaturated polyester resin.

In order to produce an FRP waterproof material and an FRP lining material, a combination of the soft unsaturated polyester resin of the present invention and a fiber reinforced material is used, and by lining and curing, curing which is excellent in flexibility and durability is achieved. You can get things. In this case, examples of the fiber reinforcement used in combination with the soft unsaturated polyester resin include organic or inorganic fiber reinforcements such as glass fiber, carbon fiber, polyester fiber, aramid fiber, vinylon fiber and metal fiber. The shape is mat, roving, cloth, chop, knitting, braiding, etc.
Generally, matt glass fibers are used. Generally, the compounding ratio of the fiber reinforcement is 15 to 80 parts by weight with respect to 100 parts by weight of the unsaturated polyester resin. Further, a filler such as calcium carbonate, aluminum hydroxide or talc, or a thermoplastic resin such as polystyrene / polyvinyl acetate or polybutadiene can be appropriately blended with the FRP waterproof material depending on the purpose.

The FRP waterproof lining material can be manufactured by a known general procedure. As an example thereof, it is possible to carry out a constitution and process such as pretreatment of a base, application / curing / drying of a primer, lining curing with FRP waterproof resin and fiber reinforcement, and application / curing of a topcoat resin. FRP waterproof lining materials can be applied to the following types of base: concrete, ALC board,
It is made of PC board, FRP, plastic, wood, metal, etc., and its shape is not particularly limited.

Materials used in combination include a primer, a putty, a top coat and the like. Examples of the primer include one-component urethane resin and vinyl ester resin. A more preferable one is selected according to the application. As the top coat, for the purpose of improving weather resistance, appearance and protection, etc., select a more preferable one from fluororesin, acrylic resin, urethane resin, acrylic silicone resin top coating, unsaturated polyester resin, etc. according to the application. Can be used.

In order to produce a resin mortar lining cured product, the soft unsaturated polyester resin of the present invention is used in combination with a filler / aggregate, and the lining is cured to obtain a cured product excellent in flexibility and durability. Obtainable. Fillers and aggregates used in combination with soft unsaturated polyester in this lining include fillers such as calcium carbonate, aluminum hydroxide, fly ash, barium sulfate, talc, clay, and glass powder, as well as silica sand and crushed stone. -Aggregates such as gravel can be used. For mortar, those having a particle size of about 5 mm or less are preferable. 100-500 parts by weight, preferably 200-400 parts by weight, of a filler and / or aggregate is mixed with 100 parts by weight of the resin. In addition, if necessary, appropriately blend organic or inorganic fiber reinforcing materials such as glass fibers, carbon fibers, polyester fibers, aramid fibers, and vinylon fibers, and thermoplastic resins such as polystyrene, polyvinyl acetate, and polybutadiene. You can

The resin mortar lining cured product can be prepared by a known general procedure. For example, pretreatment of the base, coating / curing of primer /
Drying, mixing unsaturated polyester resin and filler / aggregate to prepare and cure the lining material, and if necessary, the top coat resin can be applied / cured in a configuration / process such as coating / curing. The applicable base types of mortar lining materials are concrete, ALC plate, PC plate, F
It is made of RP, plastic, wood, metal, etc., and its shape is not particularly limited, but it is generally used on the floor surface.

As the material used in combination with the curing of the mortar lining material, a primer, a putty, a top coat and the like can be mentioned as well as the FRP waterproofing. Examples of the primer include one-component urethane resin and vinyl ester resin. A more preferable one is selected according to the application.

As a molding method for producing the FRP lining layer using the soft unsaturated polyester resin of the present invention, a hand lay-up molding method and a spray-up molding method are used. As a molding method for producing the resin mortar lining layer, a casting method, a casting method or the like is used.

Further, the unsaturated polyester resin of the present invention can be used for applications other than FRP molded article applications, resin concrete applications, resin mortar applications, FRP linings and resin mortar lining applications where surface smoothness is required. When using them, the above curing agents, accelerators,
Additives, fiber reinforcements, fillers, aggregates, thermoplastic resins and the like can be appropriately added as needed. Furthermore, as a molding method, a hand lay-up molding method, a spray-up molding method,
A filament winding molding method, a resin injection molding method, a resin transfer molding method, a pultrusion molding method, a vacuum molding method, a pressure molding method, a compression molding method, an injection molding method, a casting method, a spray method and the like can be applied.

The unsaturated polyester resin of the present invention can be used for FRP molded articles requiring surface smoothness, resin concrete applications, resin mortar applications [0075]
Doesn't it overlap with (old 0068)? ], Applications other than FRP linings and resin mortar linings include use as gel coats, paints, adhesives, decorative boards, tank containers, automobile vehicle parts, civil engineering and construction materials, and the like.

[0075]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, the synthesis conditions of the unsaturated polyester of each example and the liquid and cured physical properties of the obtained unsaturated polyester and resin were evaluated according to the following procedures.

<< Synthesis Conditions and Synthetic Results >> (1) Viscosity
It was measured according to the method of SK 6901. (2) Number average molecular weight, weight average molecular weight The polystyrene-reduced number average molecular weight and weight average molecular weight of the synthesized unsaturated polyester were measured by gel permeation chromatography (GPC). (3) Volatile Content (Radical Polymerizable Monomer Content) The unsaturated polyester resin composition obtained by synthesis was weighed in a tin plate, acetone was added and dissolved, and then heated at 110 ° C. for 2 hours. The weight was weighed, and the volatile matter was calculated from the weight reduction.

[Evaluation of Laminating Resin] <Preparation of Laminating Resin> 500 parts by weight of the resin obtained by synthesis and 10 parts by weight of a silica-based thixotropic agent (manufactured by Nippon Aireal Co., Ltd .: Aireil 200) are mixed. To the dispersed ones,
Furthermore, 500 parts by weight of the resin obtained by synthesis, 4.0 parts by weight of a 6% cobalt naphthenate solution, 0.50 parts by weight of dimethylaniline, 0.1 part of tertiary butyl catechol.
1 part by weight to 0.2 parts by weight are additionally mixed, and styrene is added if necessary, and the viscosity is 250 to 400 mPa · s and room temperature curability (25 ° C .: 1.0% by weight of a 55% by weight methyl ethyl ketone peroxide solution). % Addition) gelling time of 20 to 25 minutes was adjusted. The viscosity and thixotropy of these resins were measured according to the method of JIS K6901.

<Preparation of Test Specimens for Evaluation of Physical Properties of Cured Product> 5.0 parts by weight of a 55% by weight methyl ethyl ketone peroxide solution was mixed with 500 parts by weight of an unsaturated polyester resin as a laminating resin, and the mixture was uniformly mixed to give a thickness. It was poured into a mold assembled so as to obtain a plate-shaped cured product having a size of 4 mm, left at 25 ° C. for 16 hours for curing, and post-cured at 120 ° C. for 2 hours. A test piece was produced from this cured product by cutting according to JIS standards.

<Physical Properties of Cured Product> (1) Boiling Resistance and Heat Deformation Temperature The test pieces were subjected to a continuous boiling test at 100 ° C. according to the method of JIS K 6911 to measure the blister (swelling / crack) generation time. . Furthermore, JIS K 6
The heat distortion temperature was measured according to the 911 method. (2) Tensile Strength, Tensile Elastic Modulus, Tensile Elongation Rate The test pieces were subjected to a tensile test according to JIS K 7162 method to measure the tensile strength, the tensile elastic modulus and the tensile fracture elongation rate.

<Evaluation of FRP Laminating Workability> (1) Styrene Volatilization As the workability evaluation during FRP laminating work, the styrene volatility of the liquid resin was measured. 10 parts by weight of the modified resin for lamination was weighed in a tin cap having a diameter of 5 cm, and the weight change was measured over time in the absence of wind at 23 ° C. The styrene volatilization amount was converted into a numerical value per unit surface area / unit time from the amount of decrease in the resin and the surface area of the resin on the air surface (surface area of the resin in the tin cap). The lower the volatilization amount, the smaller the volatilization amount during actual work, and the lower the odor.

(2) Solubility of glass fiber mat As an evaluation of workability during FRP lamination work, the solubility of the glass fiber mat in the secondary binder resin was measured. Four
A 50 g / m ² glass fiber mat (manufactured by Central Glass Co., Ltd .: ECM450-198Y-CT-N / C) is cut into a strip of 3 cm × 20 cm, and the center of the glass fiber mat is placed on a horizontal table. Place the 200 on one end
Clamp the g weight and fix the other end to the base. Apply a weight (weight) to the glass fiber mat. A non-contact type displacement gauge that measures the displacement (movement) of the weight is set. Displacement measurement is started, 15 parts by weight of the liquid resin for lamination is sprayed uniformly and quickly on the central part of the glass fiber mat, and at the same time, the switch for starting the displacement meter is pressed. The time after the resin was sprayed on the glass fiber mat until the resin penetrated into the mat and the mat was cut was measured at 23 ° C. It measured 5 times. The time when it expired was read from the data of the displacement meter. The faster the solubility of the glass fiber mat (the time when the mat is cut off), the faster the glass fiber mat will be released during molding, the faster the mat will fit into the mold, and the better the workability.

(3) Impregnation of glass fiber mat with resin A black and white grid pattern sheet is placed, and transparent PET is placed thereon.
Lay the film. A glass fiber mat of 450 g / m ² (MC450-N, manufactured by Nitto Boseki Co., Ltd.) is 10 cm × 1.
Cut into a size of 0 cm, and stack three pieces on top of PET film, and place a brass ring having a diameter of 50 mm on it. Pour 5 parts by weight of liquid resin for lamination into the ring,
The time when the lower black-and-white lattice pattern started to be seen through (wet through) and the time when the inside of the ring was completely seen and the lattice pattern became visible (wet out) were measured. The shorter the wet-through time and the wet-out time, the better the impregnation property and the better the workability.

(4) Surface dryness of the laminate 5 parts by weight of the unsaturated polyester resin of the resin for lamination of 180 parts by weight.
5 wt% methyl ethyl ketone peroxide solution 1.8
Part by weight and mix uniformly, 30cm x 30cm
Resin was impregnated into a 450 g / m ² glass fiber mat (MC450-N manufactured by Nitto Boseki Co., Ltd.) cut into a size of ² mm, and ^two glass mats were stacked and laminated and cured in an atmosphere at 23 ° C. . Five hours after the lamination, the surface dryness of the laminated cured product was evaluated by touch dryness. If the surface dryness is poor, foreign matter is likely to adhere to the surface, delaying the transition to the next step and causing a problem during molding work, or causing whitening when, for example, water adheres. However, the surface performance may be deteriorated.

(5) Evaluation of surface smoothness A white gel coat resin mixed with a curing agent was wet-coated to a thickness of 0.3 mm on a 40 × 40 cm glass plate subjected to a mold release treatment and cured. After performing a post-curing treatment at 50 ° C. for 30 minutes, using a laminating resin mixed with a curing agent,
23 ° C. Glass fiber mat two 450 g / m ² in an atmosphere of, glass roving one cross 570 g / m ^2,
One 450g / m ² glass fiber mat, 570g / m
^2. Glass roving cloth No. ² One sheet was laminated and cured so that the glass content was 33 to 36% by weight. After leaving it at 23 ° C. for 16 hours, it was demolded. The surface smoothness of the gel-coated surface was measured with a comb pattern 0.5 mm by an image clarity measuring device {ICM-1DP manufactured by Suga Test Instruments Co., Ltd.} within 1 hour after demolding. Further, the same thing was measured for those that were aged at 23 ° C. for 5 days and those that were post-cured at 50 ° C. for 5 hours.

[Evaluation of resin for resin concrete molding] <Preparation of resin for resin concrete> 100 parts by weight of the resin obtained by synthesis, 2 to 10 parts by weight of styrene, 0.7 parts by weight of 8% cobalt octylate, Dimethylaniline 0.
1 to 0.2 parts by weight, tertiary butyl catechol.
A resin for resin concrete having a viscosity of 2 to 3 dPa · s and a gelling time of 20 to 25 minutes was prepared by mixing in a ratio of 005 to 0.015 part by weight. The viscosity of these resins,
Volatile content (content of radical-polymerizable monomer) was measured according to JIS method or the like.

<Preparation of Test Pieces for Evaluation of Physical Properties of Cured Product> The resin for resin concrete was mixed with 1.0 part by weight of 55% by weight methyl ethyl ketone peroxide and uniformly mixed to obtain a plate-shaped cured product having a thickness of 4 mm. To a mold assembled to obtain
It was left at 0 ° C. for 2 hours for post-curing. From this cured product J
A test piece was prepared by cutting according to the IS standard.

<Physical Properties of Cured Product> (1) Volume Shrinkage Ratio The specific gravity of the liquid resin for resin concrete and its cured product was measured according to JIS method, and the volume shrinkage ratio was measured from the measured values.

[Evaluation of general physical properties of resin concrete] <Method for producing resin concrete molded product> A liquid resin for resin concrete and a curing agent are put into a mixing mixer and mixed with stirring, and subsequently calcium carbonate, No. 7 silica sand, No. 3 silica sand, Crushed stones were added in order and mixed. This mixture was cast into a mold, defoamed for 1 minute on a vibrator, and then allowed to stand to cure.

(1) Fluidity A resin concrete composition prepared by combining the liquid resin with a filler / aggregate was used as a slump cone (upper surface diameter 4.5 cm,
Bottom diameter 6.5 cm, height 7 cm frustoconical shape), then pull out the slump cone on a smooth glass plate,
The area where the resin concrete flowed and spread in a state where it was left standing for 3 minutes was determined from the lengths in two orthogonal directions, and the value was used for the evaluation of fluidity.

(2) Bending Strength A resin concrete composition obtained by combining the liquid resin with a filler / aggregate was cast into a 6 × 6 × 24 cm rectangular parallelepiped triple die by the method specified in JIS A1184. The strength was measured according to the same regulations. (3) Compressive strength A resin concrete composition obtained by combining the liquid resin with a filler / aggregate is cast into a φ5 × 10 cm cylindrical mold by the method specified in JIS A1182, and in accordance with the same regulations. The strength was measured.

(4) Linear shrinkage ratio The resin concrete composition obtained by combining the liquid resin with the filler / aggregate was cast into a rectangular parallelepiped mold of 10 × 10 × 40 cm, and the length of the molded product with respect to the mold size was measured. The linear shrinkage was measured.

<Evaluation of Simulated Molded Product of Resin Concrete> (1) Presence or absence of cracks A flat metal mold having a width of 20 cm, a length of 80 cm and a thickness of 4 cm is formed with a convex portion at a bottom surface portion of 2 cm from both ends. When a resin concrete composition in which a liquid resin and a filler / aggregate were combined was cast and cured, the state of crack generation in the convex portion was confirmed. (2) Warp The molded product of the flat plate-shaped mold was placed on a horizontal and smooth surface, and when one side was pressed, the height at which the other end floated up was measured. (3) Appearance The appearance of the molded product formed by the flat plate-shaped mold was visually observed, and the surface gloss and color spots were compared.

[Evaluation of Resin for Lining] <Adjustment of Resin for Lining> 2000 parts by weight of unsaturated polyester resin obtained by synthesis, 0.30 part by weight of tertiary butyl catechol, 1.00 part by weight of dimethylaniline, 6 parts by weight % Cobalt naphthenate 10.0 parts by weight, 2.0 parts by weight of paraffin wax having a melting point of 52 to 54 ° C. are mixed and dissolved, and styrene is further added as necessary to make the resin viscosity 2 to 4 dPa · s for lining. The resin was adjusted.

<Evaluation of low odor and low volatility> (1) Volatility of radical-polymerizable monomer (mainly styrene) As an evaluation of workability during FRP laminating work, the radical-polymerizable monomer of liquid resin for lining was evaluated. Volatility was measured. Modified resin 10 for lamination on a tin cap with a diameter of 5 cm
Part by weight was weighed, and the change in weight was measured over time without wind at 23 ° C. Styrene volatilization amount is the reduction amount of resin and the surface area of the air surface of the resin (surface area of resin in the tin cap)
Then, it was converted into a value per unit surface area / unit time. The lower the volatilization amount, the smaller the volatilization amount during the actual work, and the lower odor becomes possible.

<Preparation of Test Pieces for Evaluation of Physical Properties of Cast Cured Products>
A mold assembled so that 5.0 parts by weight of a curing agent (55% by weight methyl ethyl ketone peroxide solution) is mixed with 500 parts by weight of the lining resin and uniformly mixed to obtain a plate-like cured product having a thickness of 4 mm. Then, the mixture was cast and cured, and left at 25 ° C. for 7 days to cure and cure. JIS from this cured product
A test piece was prepared by cutting in accordance with the standard.

<Physical Properties of Cast Cured Products> (1) Tensile Strength, Tensile Elastic Modulus, and Tensile Elongation Rate The tensile strength, tensile elastic modulus, and tensile elongation at break of the test pieces were measured according to JIS method. did. (2) Continuous boiling test The above-mentioned test piece was subjected to a continuous boiling test at 100 ° C according to JIS method to observe the appearance change, and the time until blister was generated was measured.

<Performance Evaluation of FRP Waterproof Material> (1) Accelerated Deterioration Test For the test pieces, JIS A 6021 method and “FR
P waterproof construction guideline (draft) and the same explanation ”, heat treatment (80 ° C oven 168 hours) and accelerated exposure treatment (250 hours), alkali treatment (0.1% sodium hydroxide / calcium hydroxide saturated aqueous solution 23 ° C 168) Time), acid treatment (2% sulfuric acid aqueous solution 23 ° C. 168 hours)
The tensile test of the test piece after carrying out was carried out, and the tensile strength and the tensile elongation were measured. Regarding heat treatment, alkali treatment, and acid treatment, tests up to 2 weeks were also conducted.

(2) Adhesion test The oil content and the latance on the upper surface of a dry concrete plate (sidewalk plate) having a size of 30 cm × 30 cm and a thickness of 5 cm were removed, and a one-component urethane primer {UM-50
P (manufactured by Showa Highpolymer Co., Ltd.)} 30 parts by weight 0.2 kg /
m ² was applied and left for 3 hours to dry. Subsequently, 50 parts by weight of the lining resin and 0.5 part by weight of a curing agent (55% by weight methyl ethyl ketone peroxide solution) on top of this.
Add 4 parts by weight and mix, then add 0.4 on the concrete board.
Coating with 1 kg / m ² and curing, then resin for lining 1
1.6 parts by weight of the curing agent was added to 60 parts by weight and mixed to obtain 3 parts.
450 g / m ² glass fiber mat cut into a size of 0 cm x 30 cm (Nitto Boseki Co., Ltd .: MC450-N)
Was used to lining and cure while impregnating the resin.

Further, on top of that, 1.5 parts by weight of a gray toner, 50 parts by weight of a lining resin, and a curing agent of 0.
5 parts by weight were added, mixed, coated and cured. After curing for 4 hours, the paraffin wax layer on the surface was removed by polishing, and 48 parts by weight of an acrylic urethane paint-based topcoat resin (PCG 6M263: manufactured by Tokyo Ink Co., Ltd.) was added to the curing agent (PCG 1M217: Tokyo Ink). (Manufactured by K.K.) 6 parts by weight were mixed and applied. After curing for 7 days, make a notch in the lining layer with a square size of 40 mm on a side, lightly polish the surface, and then use vinyl ester resin (lipoxy RT-833DA: Showa Highpolymer Co., Ltd.) 40mm x 40mm using a mixture of cobalt-based accelerator, dimethylaniline, and curing agent.
A steel jig of the same size was adhered and fixed to the surface. After 24 hours, a Kenken tester (R-1 manufactured by Nagano Keiki Seisakusho Co., Ltd.)
000), the steel jig was peeled off, and the adhesive strength and the fracture mode were measured.

<Performance Evaluation of Mortar Lining Layer> (1) Strength Test and Chemical Resistance Test 5.0 parts by weight of a curing agent (55% by weight methyl ethyl ketone peroxide solution) was mixed with 500 parts by weight of the resin for lining and uniformly added. And 280 parts by weight of calcium carbonate (SS # 30 manufactured by Nitto Koka Kogyo Co., Ltd.), 700 parts by weight of silica sand No. 7, and 420 parts by weight of silica sand No. 4 were uniformly mixed to obtain 40 cm × 40 cm × 0. It was poured into a 5 cm mold and cured. It was left to stand at 25 ° C. for 7 days to be cured and cured. A test piece was produced from this cured product by cutting according to JIS standards. A bending test and a compression test were carried out in accordance with the test standard of JIS K 6911, and the bending strength and the compression strength were measured.
A chemical resistance test was carried out by immersing in a 0.1% and 1.0% sodium hydroxide aqueous solution at 60 ° C. The change in appearance and the change in weight were measured after 7 days and 14 days.

(2) Adhesion test The oil component / latency etc. on the upper surface of a concrete plate having a size of 30 cm × 30 cm and a thickness of 5 cm was removed, and a one-component urethane primer {UM-50P (Showa Polymer Co., Ltd. ))) 30 parts by weight are applied at 0.2 kg / m ² ,
It was left to dry for 3 hours. Subsequently, 220 parts by weight of the resin for lining and 3.3 parts by weight of the curing agent are mixed and uniformly mixed, and 125 parts by weight of calcium carbonate, 310 parts by weight of silica sand No. 7, and 185 parts by weight of silica sand No. 4 are further added. After uniform mixing, the mortar was lined and cured while removing bubbles. Further on, lining resin 5
0 parts by weight of gray toner 1.5 parts by weight, curing agent 0.5
Parts by weight were added, mixed, applied and cured. After curing at room temperature for 7 days, the adhesive strength and the fracture mode were measured with a Kenken tensile tester as with the FRP waterproof material.

(3) Impact Test A 535 g steel ball was dropped onto the cured lining material from a height of 2 m, and the presence or absence of peeling or cracks in the lining layer was confirmed.

<< Synthesis of Resin >> (Synthesis Example 1) 1548 parts by weight of dicyclopentadiene and 212 parts by weight of water were charged in a 10-liter flask equipped with a stirrer, a fractionating condenser, a thermometer, and a nitrogen introducing tube.
While heating and stirring under a nitrogen stream, 1150 parts by weight of maleic anhydride was added in 4 divided portions at 60 ° C. to 100 ° C. while reacting with the exothermic reaction, followed by reaction.
Dicyclopentadiene maleate and dicyclopentadiene fumarate were synthesized by reacting at 40 ° C. for 2 hours, then 952 parts by weight of benzyl alcohol and 1726 parts by weight of maleic anhydride were charged, and while paying attention to heat generation from 60 ° C. to 120 ° C. The esterification reaction was carried out for 1 hour, 1942 parts by weight of propylene glycol was further charged, and the esterification reaction was carried out at 150 ° C. to 220 ° C. according to a standard procedure. When the acid value reached 25.7 mgKOH / g, the mixture was cooled and the unsaturated polyester 7000 was added. Parts by weight were obtained. As a result of measuring the molecular weight of this polyester by GPC, the number average molecular weight in terms of polystyrene was 680, and the weight average molecular weight was 1410.
Met. Next, 1.0 part by weight of hydroquinone was added to 7000 parts by weight of this unsaturated polyester and dissolved in 3000 parts by weight of styrene to prepare an unsaturated polyester resin (R-1). The viscosity of this resin (25 ℃) is 1
It was 50 mPa · s.

(Synthesis Example 2) By the same method as in Example 1,
1902 parts by weight of dicyclopentadiene and 260 parts by weight of water were charged, and the mixture was heated at 60 ° C. under a nitrogen stream while stirring to 1 ° C.
At 00 ° C, 1414 parts by weight of maleic anhydride were added in 4 portions while paying attention to the exothermic reaction, and the reaction was continued.
Dicyclopentadiene maleate and dicyclopentadiene fumarate are synthesized by reacting at 0 ° C to 140 ° C for 2 hours, and 624 parts by weight of benzyl alcohol and 1414 parts by weight of maleic anhydride are charged, and the mixture is heated at 60 ° C to 120 ° C.
The esterification reaction was carried out for 1 hour while paying attention to the heat generation, and 1908 parts by weight of propylene glycol was further charged.
An esterification reaction was carried out at a temperature of 50 ° C. to 220 ° C. by a standard procedure, and when the acid value reached 23.7 mgKOH / g, the mixture was cooled to obtain 7000 parts by weight of unsaturated polyester. As a result of measuring the molecular weight of this polyester by GPC, the number average molecular weight in terms of polystyrene was 690 and the weight average molecular weight was 1530. Next, 1.0 part by weight of hydroquinone was added to 7000 parts by weight of this unsaturated polyester and dissolved in 3000 parts by weight of styrene to obtain a viscosity (2
An unsaturated polyester resin (R-2) having a temperature of 5 ° C. of 220 mPa · s was prepared.

(Synthesis Example 3) By the same method as in Example 1,
1272 parts by weight of dicyclopentadiene and 174 parts by weight of water were charged, and the mixture was heated from 60 ° C. to 1 while stirring under heating in a nitrogen stream.
At 00 ° C, 946 parts by weight of maleic anhydride were added in 4 portions while paying attention to the exothermic reaction, and the reaction was continued.
Dicyclopentadiene maleate and dicyclopentadiene fumarate are synthesized by reacting at ℃ to 140 ℃ for 2 hours, 522 parts by weight of benzyl alcohol and 630 parts by weight of maleic anhydride are charged, and heat is generated from 60 ℃ to 120 ℃. Carefully carry out the esterification reaction for 1 hour, and further add 920 parts by weight of neopentyl glycol and bisphenol A.
Propylene adduct of {Adeca polyether BPX-1
1: Molecular weight 355; Asahi Denka Co., Ltd.} 1426 parts by weight were charged, and esterification reaction was carried out at 150 ° C. to 220 ° C. according to a standard procedure to cool when the acid value reached 26.2 mg KOH / g, and the unsaturated polyester 3500 parts by weight were obtained. As a result of measuring the molecular weight of this polyester by GPC, the molecular weight in terms of polystyrene is 965.
However, the weight average molecular weight was 1780. Next, 1.0 part by weight of hydroquinone was added to 7000 parts by weight of this unsaturated polyester and dissolved in 3000 parts by weight of styrene to obtain an unsaturated polyester resin (R-3) having a viscosity (25 ° C.) of 370 mPa · s. Prepared.

(Synthesis Example 4) In the same manner as in Synthesis Example 1,
Tricyclopentadiene [Maruzen Petrochemical Co., Ltd .: molecular weight 198] 3664 parts by weight and water 333 parts by weight were charged,
While heating and stirring under a nitrogen stream, 1812 parts by weight of maleic anhydride were added in 4 divided portions at 60 ° C to 100 ° C while reacting with an exothermic reaction, followed by reaction at 120 ° C to 1 ° C.
Reaction is carried out at 40 ° C. for 2 hours to synthesize tricyclopentadiene maleate and / or fumarate, 353 parts by weight of benzyl alcohol and 320 parts by weight of maleic anhydride are charged, and 1 to 40 ° C. to 120 ° C. while paying attention to heat generation.
After the esterification reaction for 10 hours, 1023 parts by weight of propylene glycol was charged, and the esterification reaction was carried out at 150 ° C. to 220 ° C. according to a standard procedure to obtain an acid value of 19.0 m.
When it reached gKOH / g, it was cooled and the number average molecular weight was 6
40, unsaturated polyester 7 having a weight average molecular weight of 970
000 parts by weight was obtained. Next, this unsaturated polyester 7
Add 1.0 parts by weight of hydroquinone to 000 parts by weight,
Dissolved in 3000 parts by weight of styrene, viscosity (25 ℃)
The unsaturated polyester resin (R-4) having a viscosity of 360 mPa · s was prepared.

(Synthesis Example 5) Stirrer, fractionating condenser,
In a 5 liter flask equipped with a thermometer and a nitrogen inlet tube,
Polypropylene glycol {Adeca polyether P-4
00: molecular weight 400, manufactured by Asahi Denka Co., Ltd.} 4958 parts by weight and 916 parts by weight of isophthalic acid were charged, and an esterification reaction was carried out at 180 ° C. to 230 ° C. under heating and stirring under a nitrogen stream, and an acid value was 4.6 mgKOH. / G, the mixture was cooled to obtain an esterified product of isophthalic acid. Separately, 728 parts by weight of dicyclopentadiene and 108 parts by weight of water are charged, and 540 parts by weight of maleic anhydride is divided into 4 parts while paying attention to heat generation, 60 ° C to 100 ° C is charged to synthesize maleic acid, and further 120 ° C to 140 ° C. 2 hours to react to synthesize dicyclopentadiene malate and dicyclopentadiene fumarate.
Charge 94 parts by weight and 810 parts by weight of maleic anhydride, and
The reaction is carried out at 00 ° C to 150 ° C for 1 hour, the esterified product of isophthalic acid synthesized above is charged, and the esterification reaction is carried out at 150 ° C to 220 ° C by a standard procedure.
When the acid value reached 24.9 mgKOH / g, the mixture was cooled to obtain 8500 parts by weight of unsaturated polyester. As a result of measuring the molecular weight of this polyester by GPC, the polystyrene reduced molecular weight was 1210 in number average molecular weight and 2990 in weight average molecular weight. Next, 0.5 part by weight of hydroquinone was added to 8500 parts by weight of this unsaturated polyester, and dissolved in 1500 parts by weight of styrene to obtain a viscosity (25
C) is 820 mPa · s unsaturated polyester resin (R
-5) was prepared.

(Synthesis Example 6) In the same manner as in Example 1,
Polypropylene glycol {Adeca polyether P-4
00: molecular weight 400, Asahi Denka Co., Ltd.} 5062 parts by weight, isophthalic acid 934 parts by weight were charged, and the esterification reaction was carried out at 180 ° C to 230 ° C while heating and stirring under a nitrogen stream, and the acid value was 5.5 mgKOH. / G, the mixture was cooled to obtain an esterified product of isophthalic acid. Separately, 186 parts by weight of dicyclopentadiene and 28 parts by weight of water are charged, and 138 parts by weight of maleic anhydride is divided into 4 parts while paying attention to heat generation, 60 ° C to 100 ° C is charged to synthesize maleic acid, and further 120 ° C to 140 ° C. 2 hours to react to synthesize dicyclopentadiene malate and dicyclopentadiene fumarate.
368 parts by weight and 1240 parts by weight of maleic anhydride were charged and reacted at 100 ° C. to 150 ° C. for 1 hour, and then the esterified product of isophthalic acid synthesized earlier was charged.
An esterification reaction was carried out at a temperature of 0 ° C to 220 ° C by a standard procedure, and when the acid value reached 28.3 mgKOH / g, the mixture was cooled to obtain 8500 parts by weight of unsaturated polyester. As a result of measuring the molecular weight of this polyester by GPC, the number average molecular weight in terms of polystyrene was 1180 and the weight average molecular weight was 2840. Next, 0.58 parts by weight of hydroquinone was added to 8500 parts by weight of this unsaturated polyester and dissolved in 1500 parts by weight of styrene to obtain an unsaturated polyester resin (R-6) having a viscosity (25 ° C.) of 380 mPa · s. Prepared.

(Synthesis Example 7) By the same method as in Synthesis Example 1,
1026 parts by weight of benzyl alcohol and 580 parts by weight of 2-aminoethanol were charged, and tetrahydrophthalic anhydride 1 was added at 0 ° C. to 100 ° C. while heating and stirring under a nitrogen stream.
444 parts by weight were added while paying attention to heat generation, and an amidation reaction was carried out, followed by a dehydration reaction at 120 ° C. to 170 ° C. for imidization. Further, 2232 parts by weight of maleic anhydride was charged and reacted at 80 ° C. to 120 ° C. for 1 hour, subsequently 1560 parts by weight of propylene glycol and 844 parts by weight of phthalic anhydride were charged, and the ester was prepared at 150 ° C. to 220 ° C. by a standard procedure. The acid value is 33.5.
When the amount reached mgKOH / g, the mixture was cooled to obtain 7000 parts by weight of unsaturated polyester. As a result of measuring the molecular weight of this polyester by GPC, the number average molecular weight in terms of polystyrene was 630 and the weight average molecular weight was 940. Next, 1.0 part by weight of hydroquinone was added to 7000 parts by weight of this unsaturated polyester and dissolved in 3000 parts by weight of styrene to obtain an unsaturated polyester resin (R-7) having a viscosity (25 ° C.) of 165 mPa · s. Prepared.

(Synthesis Example 8) In the same manner as in Synthesis Example 1,
909 parts by weight of benzyl alcohol and 513 parts by weight of 2-aminoethanol were charged, and tetrahydrophthalic anhydride 12 was added at 0 ° C. to 100 ° C. while heating and stirring under a nitrogen stream.
79 parts by weight were added while paying attention to heat generation, and an amidation reaction was carried out, followed by a dehydration reaction at 120 ° C. to 170 ° C. for imidization. Furthermore, 1279 parts by weight of maleic anhydride was charged and reacted at 80 to 120 ° C. for 1 hour, and then a propylene adduct of bisphenol A {Adeka Polyether BPX-11: Molecular weight 355; Asahi Denka Co., Ltd.
3103 parts by weight were charged, and the esterification reaction was carried out at 150 ° C. to 220 ° C. according to a standard procedure to obtain an acid value of 30.1.
When the amount reached mgKOH / g, the mixture was cooled to obtain 7000 parts by weight of unsaturated polyester. As a result of measuring the molecular weight of this polyester by GPC, the polystyrene reduced molecular weight was number average molecular weight 610 and weight average molecular weight 920. Next, to 7,000 parts by weight of this unsaturated polyester, 1.0 part by weight of hydroquinone was added, and styrene 3000 was added.
When dissolved in parts by weight, the viscosity (25 ° C) is 305 mPa.
An unsaturated polyester resin (R-8) of s was prepared.

(Synthesis Example 9) By the same method as in Synthesis Example 1,
1416 parts by weight of benzyl alcohol and 88 parts by weight of 2-aminoethanol were charged, and 224 parts by weight of hexahydrophthalic anhydride {Ricacid HH: manufactured by Shin Nippon Rika Co., Ltd.} was added at 30 ° C to 100 ° C while paying attention to heat generation. To perform an amidation reaction, and a dehydration reaction at 120 ° C. to 150 ° C. for imidization. Further, maleic anhydride 142
6 parts by weight were charged and reacted at 60 ° C. to 120 ° C. for 1 hour, and then a propylene adduct of bisphenol A {Adeca polyether BPX-55: molecular weight 773.
8, Asahi Denka Co., Ltd.} 5630 weight was charged, 150 ℃
To 220 ° C., an esterification reaction was carried out by a standard procedure, and when the acid value reached 28.1 mgKOH / g, the mixture was cooled to obtain 8500 parts by weight of an unsaturated polyester having a number average molecular weight of 870 and a weight average molecular weight of 2280. Next, 0.58 parts by weight of this unsaturated polyester was added to 0.5 parts of hydroquinone.
One part by weight was added and dissolved in 1500 parts by weight of styrene to prepare an unsaturated polyester resin (R-9) having a viscosity (25 ° C.) of 670 mPa · s.

(Synthesis Example 10) In the same manner as in Synthesis Example 1, 742 parts by weight of benzyl alcohol and 418 parts by weight of 2-aminoethanol were charged, and hexahydrophthalic anhydride {Ricacid HH: Shin 1058 parts by weight of Nippon Rika Co., Ltd. was added while paying attention to heat generation, and an amidation reaction was carried out. Further, a dehydration reaction was carried out at 120 ° C. to 150 ° C. for imidization. Furthermore, maleic anhydride 1
344 parts by weight were charged and the reaction was carried out at 60 to 120 ° C. for 1 hour, and then a propylene adduct of bisphenol A {Adeca polyether BPX-55: molecular weight 773.
8, Asahi Denka Co., Ltd.} 5306 weight was charged, 150
C. to 220.degree. C., the esterification reaction was carried out by a standard procedure, and when the acid value reached 15.1 mgKOH / g, the mixture was cooled and the number average molecular weight was 960 and the weight average molecular weight was 2460.
8500 parts by weight of unsaturated polyester were obtained. Next, 0.58 parts by weight of hydroquinone was added to 8500 parts by weight of this unsaturated polyester and dissolved in 1500 parts by weight of styrene to obtain an unsaturated polyester resin (R-10) having a viscosity (25 ° C.) of 890 mPa · s. Prepared.

(Synthesis Example 11) In the same manner as in Synthesis Example 1, 392 parts by weight of 2-aminoethanol was charged, and the mixture was heated and stirred under a nitrogen stream at 0 to 100 ° C. and 974 parts by weight of tetrahydrophthalic anhydride. Is added while paying attention to heat generation, and the amidation reaction is continued.
A dehydration reaction was performed at ℃ to imidize. Further, 628 parts by weight of maleic anhydride was charged, and the mixture was reacted at 60 ° C. to 120 ° C. for 1 hour, and further, a propylene adduct of bisphenol A {Adeca polyether BPX-11: molecular weight 35
5; Asahi Denka Co., Ltd.} 2364 parts by weight and 1590 parts by weight of dicyclopentadiene maleate were charged, and the esterification reaction was carried out at 150 ° C. to 220 ° C. by a standard procedure, and when the acid value became 31.0 mg KOH / g. After cooling, 7,000 parts by weight of unsaturated polyester was obtained. As a result of measuring the molecular weight of this polyester by GPC, the polystyrene-reduced number average molecular weight was 770 and the weight average molecular weight was 1310. Next, 1.0 part by weight of hydroquinone was added to 7000 parts by weight of this unsaturated polyester to prepare styrene 3
Dissolved in 000 parts by weight, viscosity (25 ℃) 410m
A Pa · s unsaturated polyester resin (R-11) was prepared.

(Synthesis Example 12) In the same manner as in Synthesis Example 1, 580 parts by weight of 2-aminoethanol was charged, and 1446 parts by weight of tetrahydrophthalic anhydride at 0 ° C to 100 ° C under heating and stirring under a nitrogen stream. Is added while paying attention to heat generation, and the amidation reaction is carried out.
A dehydration reaction was performed at 0 ° C. for imidization. Furthermore, 932 parts by weight of maleic anhydride was charged, and the mixture was heated at 60 to 120 ° C for 1 hour.
After reacting for a period of time, 796 parts by weight of propylene glycol and 2358 parts by weight of dicyclopentadiene maleate were charged, and the esterification reaction was carried out at 150 ° C. to 220 ° C. according to a standard procedure until the acid value became 31.2 mg KOH / g. After cooling, 7,000 parts by weight of unsaturated polyester was obtained. As a result of measuring the molecular weight of this polyester by GPC, the polystyrene-reduced number average molecular weight was 640 and the weight average molecular weight was 1080. Next, to 7000 parts by weight of this unsaturated polyester, 1.0 part by weight of hydroquinone was added and dissolved in 3000 parts by weight of styrene to obtain an unsaturated polyester resin (R-12) having a viscosity (25 ° C.) of 230 mPa · s. Prepared.

(Synthesis Example 13) In the same manner as in Synthesis Example 1, 406 parts by weight of 2-aminoethanol was charged, and 30
From 102 ° C to 100 ° C, 1022 parts by weight of hexahydrophthalic anhydride {Ricacid HH: manufactured by Shin Nippon Rika Co., Ltd.} was added while paying attention to heat generation, and the amidation reaction was further performed.
Imidization was carried out by dehydration reaction at 150 ° C to 150 ° C. Further, 650 parts by weight of maleic anhydride was charged and reacted at 100 ° C. to 150 ° C. for 1 hour, then 1726 parts by weight of dicyclopentadiene maleate and a propylene adduct of bisphenol A {Adeca polyether BPX-55: molecular weight 773.8. , Manufactured by Asahi Denka Co., Ltd.} 5134 weights were charged, the esterification reaction was carried out at 150 ° C. to 220 ° C. by a standard procedure, and the mixture was cooled when the acid value reached 17.2 mg KOH / g, and the number average molecular weight was 880, the weight average. 8500 parts by weight of unsaturated polyester having a molecular weight of 1840 were obtained.
Next, 0.5 parts by weight of hydroquinone was added to 8500 parts by weight of this unsaturated polyester and dissolved in 1500 parts by weight of styrene to obtain an unsaturated polyester resin (R-13) having a viscosity (25 ° C.) of 920 mPa · s. Prepared.

(Comparative Synthesis Example 1) In the same manner as in Synthesis Example 1, 3484 parts by weight of dicyclopentadiene and 475 parts by weight of water were charged, and maleic anhydride was heated at 60 ° C. to 100 ° C. while heating and stirring under a nitrogen stream. While paying attention to the exothermic reaction, 2464 parts by weight were added in 4 portions and the reaction was carried out, followed by reacting at 120 ° C. to 140 ° C. for 2 hours to synthesize dicyclopentadiene maleate and dicyclopentadiene fumarate. 1052 parts by weight were charged, and esterification reaction was carried out at 150 ° C. to 220 ° C. according to a standard procedure. When the acid value reached 26.4 mgKOH / g, the mixture was cooled, and an unsaturated polyester having a number average molecular weight of 530 and a weight average molecular weight of 1280 7,000 parts by weight were obtained. Next, 0.50 parts by weight of hydroquinone was added to 7000 parts by weight of this unsaturated polyester to prepare styrene 30
When dissolved in 00 parts by weight, the viscosity (25 ° C) is 190 mP
An as unsaturated polyester resin (UP-1) was prepared.

(Comparative Synthesis Example 2) In the same manner as in Synthesis Example 1, 2944 parts by weight of propylene glycol, 3274 parts by weight of phthalic anhydride and 1446 parts by weight of maleic anhydride were charged in a one-step reaction method to carry out an esterification reaction to obtain an acid. Price 38.5m
7000 parts by weight of an unsaturated polyester having gKOH / g, a number average molecular weight of 1810 and a weight average molecular weight of 3,200 was obtained. To 7000 parts by weight of this unsaturated polyester, 1.0 part by weight of hydroquinone was added and dissolved in 3000 parts by weight of styrene to prepare an unsaturated polyester resin (UP-2) having a viscosity (25 ° C.) of 1420 mPa · s.

(Comparative Synthesis Example 3) In the same manner as in Synthesis Example 1, 3636 parts by weight of propylene glycol, 1572 parts by weight of phthalic anhydride and 2430 parts by weight of maleic anhydride were charged in a one-step reaction method to carry out an esterification reaction to obtain an acid. Price 32.5m
7,000 parts by weight of unsaturated polyester having gKOH / g, a number average molecular weight of 990 and a weight average molecular weight of 1610 were obtained. To 7000 parts by weight of this unsaturated polyester, 1.0 part by weight of hydroquinone was added and dissolved in 3000 parts by weight of styrene to prepare an unsaturated polyester resin (UP-3) having a viscosity (25 ° C.) of 350 mPa · s.

(Comparative Synthesis Example 4) In the same manner as in Synthesis Example 1,
Charge 2076 parts by weight of 2-ethylhexanol to 60
At 1 ℃ to 100 ℃, add 1562 parts by weight of maleic anhydride, paying attention to the exothermic reaction, and react.
React for 1 hour at propylene glycol 189
2 parts by weight, 1416 parts by weight of phthalic anhydride, and 626 parts by weight of maleic anhydride were charged and an esterification reaction was carried out to obtain an unsaturated polyester 7000 having an acid value of 31.6 mgKOH / g, a number average molecular weight of 875 and a weight average molecular weight of 1670.
Parts by weight were obtained. To 7000 parts by weight of this unsaturated polyester, 1.0 part by weight of hydroquinone was added, and styrene 30
When dissolved in 00 parts by weight, the viscosity (25 ° C) is 80 mPa
-S unsaturated polyester resin (UP-4) was prepared.

(Comparative Synthesis Example 5) In the same manner as in Synthesis Example 1,
1802 parts by weight of benzyl alcohol was charged, and 1632 parts by weight of maleic anhydride was added while reacting with heating and stirring under a nitrogen stream at 60 ° C to 100 ° C while reacting, and subsequently reacted at 120 ° C for 1 hour. Further, 2028 parts by weight of propylene glycol, 656 parts by weight of maleic anhydride and 1480 parts by weight of phthalic anhydride were charged, and an esterification reaction was carried out at 150 ° C to 220 ° C to obtain an acid value of 31.0 mgKOH / g and a number average molecular weight of 73.
0, unsaturated polyester 7 having a weight average molecular weight of 1430
000 parts by weight was obtained. Next, 1.0 part by weight of hydroquinone was added to 7000 parts by weight of this unsaturated polyester and dissolved in 3000 parts by weight of styrene to obtain a viscosity (25
Unsaturated polyester resin (U) of 105 mPa · s (U
P-5) was prepared.

(Comparative Synthesis Example 6) In the same manner as in Synthesis Example 1,
An acid value of 4.4 mgK was obtained by charging 3428 parts by weight of dipropylene glycol and 3396 parts by weight of isophthalic acid.
After cooling with OH / g, 702 parts by weight of maleic anhydride was charged, and the esterification reaction was carried out in the same manner to obtain an acid value of 2
6500 parts by weight of unsaturated polyester having 4.4 mgKOH / g, a number average molecular weight of 2110 and a weight average molecular weight of 7,200 was obtained. To 6500 parts by weight of this unsaturated polyester, 1.0 part by weight of hydroquinone was added, and styrene 350 was added.
When dissolved in 0 parts by weight, the viscosity (25 ° C) is 590 mPas.
-S unsaturated polyester resin (UP-6) was prepared.

(Comparative Synthesis Example 7) In the same manner as in Synthesis Example 1, 1868 parts by weight of dipropylene glycol, 1492 parts by weight of diethylene glycol and 2544 parts by weight of isophthalic acid were charged and reacted to cool at an acid value of 3.5 mgKOH / g. Then, 970 parts of fumaric acid and 610 parts of adipic acid were continuously charged to carry out an esterification reaction to obtain an acid value of 27.6 mg.
7,000 parts by weight of unsaturated polyester having KOH / g, a number average molecular weight of 2860 and a weight average molecular weight of 8400 were obtained. To 7000 parts by weight of this unsaturated polyester, 1.0 part by weight of hydroquinone was added and dissolved in 3000 parts by weight of styrene to prepare an unsaturated polyester resin (UP-7) having a viscosity (25 ° C.) of 740 mPa · s.

(Comparative Synthesis Example 8) In the same manner as in Synthesis Example 1, polypropylene glycol {Adeca polyether P-40 was used.
0: molecular weight 400, Asahi Denka Co., Ltd.} 2616 parts by weight,
1754 parts by weight of dipropylene glycol and 1086 parts by weight of isophthalic acid were charged, and an esterification reaction was carried out at 150 ° C to 230 ° C. When the acid value became 3 mgKOH / g or less, 1704 parts by weight of octanol and 2280 parts of fumaric acid were further added. Was added to carry out an esterification reaction, the acid value was 29.5 mgKOH / g, the number average molecular weight was 1020,
Unsaturated polyester 850 having a weight average molecular weight of 2310
0 parts by weight were obtained. To 1,500 parts by weight of this unsaturated polyester, 0.5 parts by weight of hydroquinone was added to give 1 part of styrene.
Dissolved in 500 parts by weight, viscosity (25 ℃) is 490m
A Pa · s unsaturated polyester resin (UP-8) was prepared.

Comparative Example 9 By the same method as in Synthesis Example 1,
Benzyl alcohol 1208 parts by weight, fumaric acid 186
8 parts by weight were charged, the esterification reaction was carried out at 150 ° C to 190 ° C for 3 hours, and polyethylene glycol {Toho polyethylene glycol # 400: molecular weight 40 was added.
0, manufactured by Toho Chemical Industry Co., Ltd.} 4470 parts by weight, dipropylene glycol 750 parts by weight, and isophthalic acid 928 parts by weight were charged, and an esterification reaction was carried out at 150 ° C. to 220 ° C. according to a standard procedure to obtain an acid value of 28.7 mgKOH / g
When cooled, the mixture was cooled to obtain 8500 parts by weight of unsaturated polyester having a number average molecular weight of 890 and a weight average molecular weight of 1930. Next, 0.58 parts by weight of hydroquinone was added to 8500 parts by weight of this unsaturated polyester to prepare styrene 15
When dissolved in 00 parts by weight, the viscosity (25 ° C) is 430 mP.
An as unsaturated polyester resin (UP-9) was prepared.

(Comparative Example 10) In the same manner as in Synthesis Example 1, 2608 parts by weight of dicyclopentadiene and 356 parts by weight of water were charged, and 1938 parts by weight of maleic anhydride were divided into 4 parts from 60 ° C while paying attention to heat generation. Maleic acid was synthesized at 100 ° C., further reacted at 120 ° C. to 140 ° C. for 2 hours to synthesize dicyclopentadiene maleate and dicyclopentadiene fumarate, and further polypropylene glycol {Adeca polyether P-400: molecular weight 400 ,
Asahi Denka Co., Ltd.} 3952 parts by weight was charged and the esterification reaction was carried out at 150 ° C. to 220 ° C. according to a standard procedure.
When the acid value reaches 24.9 mgKOH / g, cooling is carried out,
8500 parts by weight of unsaturated polyester having a polystyrene equivalent number average molecular weight of 750 and a weight average molecular weight of 1790 was obtained. Next, 0.58 parts by weight of hydroquinone was added to 8500 parts by weight of this unsaturated polyester to prepare styrene 15
Dissolved in 00 parts by weight, viscosity (25 ° C) is 240 mP
An as unsaturated polyester resin (UP-10) was prepared.

<< resin synthesis results >> The results of the resins obtained in the synthesis examples and comparative synthesis examples are shown in Table 1.

[0127]

[Table 1]

Examples 1 to 8 and Comparative Examples 1 to 5 The synthetic resin was used to modify the laminating resin, and the FRP molding resin was evaluated. The blending results and evaluation results are shown in Tables 2 and 3.

[0129]

[Table 2]

[0130]

[Table 3]

Regarding the numerical value of the image clarity of the surface smoothness, the higher the numerical value, the better the result is, and the smaller the decrease with the passage of time, the better the appearance. 1 hour after demolding, 5 days later, and 50 ° C./5 hours later, there was little decrease in the numerical values, and higher values indicate better surface properties.

[0132]

[Table 4]

(Examples 14 to 18 and Comparative Examples 6 to 8)
Synthetic resin and polystyrene low shrinkage agent {M-5585
Showa Highpolymer Co., Ltd. solid content 30% styrene solution}, silane compound (silane coupling agent) {trimethoxy γ-methacryloxypropylsilane: Shin-Etsu Chemical Co., Ltd. KBM-503}, The resin for resin concrete was modified with the composition shown in Table 3 to evaluate the resin for resin concrete. Table 4 shows these compounding results and evaluation results.

[0134]

[Table 5] The figures of the compounding ratio represent the weight ratio. As the curing agent, 55% methyl ethyl ketone peroxide {Perfex N manufactured by NOF CORPORATION) was used.

[0135]

[Table 6]

(Examples 19 to 23 and Comparative Examples 9 to 1)
3) The synthetic resin was used to modify the lining resin, and the lining resin, the FRP waterproof material, and the mortar lining material were evaluated. The blending results and evaluation results are shown in Table 7, Table 8, Table 10, Table 11, Table 13, and Table 14.

[0137]

[Table 7]

[0138]

[Table 8]

[0139]

[Table 9]

[0140]

[Table 10]

[0141]

[Table 11] Strength: Tensile strength Elongation rate: Tensile fracture elongation rate The result was evaluated by the retention rate against the value before the accelerated deterioration test.

[0142]

[Table 12]

[0143]

[Table 13] The chemical resistance number indicates the value of the rate of weight change after immersion in an alkaline aqueous solution at 60 ° C. (unit:%)

[0144]

[Table 14] The chemical resistance number indicates the value of the rate of weight change after immersion in an alkaline aqueous solution at 60 ° C. (unit:%)

[0145]

[Table 15]

[0146]

INDUSTRIAL APPLICABILITY The present invention provides an unsaturated polyester used for an unsaturated polyester resin, wherein the molecular terminal group has an acid imide alcohol residue, an alkyl alcohol residue having one or more phenyl groups, and dicyclopentadienyl and And / or an invention, which comprises developing an unsaturated polyester containing at least two residues from the group consisting of oligocyclopentadienyl residues and a method for producing the same, and using the same as an unsaturated polyester resin. is there. ADVANTAGE OF THE INVENTION According to this invention, since the content of the radically polymerizable monomer at the time of lining work in the field in FRP molding work and resin concrete molding work, FRP waterproofing, and resin mortar lining can be reduced, the effect of improving a work environment and reducing odor is achieved. It is possible to give a cured product having excellent flexibility and durability (heat treatment, accelerated exposure treatment, alkali treatment, acid treatment, water resistance). An unsaturated polyester used in the unsaturated polyester resin composition, a method for producing the same, and an unsaturated polyester resin composition having the above properties can be provided,
Further, the present invention provides an FRP waterproof material and a mortar lining cured product which are obtained by using the unsaturated polyester resin and have excellent flexibility and durability, and a method for producing the same.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 7/02 C08K 7/02 C08L 55/00 C08L 55/00 (72) Inventor Tetsuya Kubo Isesaki City, Gunma Prefecture Naganuma 602-183-12 F Term (Reference) 4F072 AA02 AB04 AB05 AB06 AB09 AB10 AB11 AD38 AF03 AF04 AF06 AK11 AK12 AK13 AK14 AK15 AK17 AK20 AL01 AL09 AL17 4J002 BD102 BE063 DJ036 DJ036 DJ036 DJ036DE037 DL006 DL007 FA043 FA047 FA102 FA106 GL00 GL02 4J027 AB06 AB15 AB17 AB18 AB23 AB24 AB25 AB26 AB32 BA03 BA05 BA07 BA13 BA18 BA20 BA23 BA26 CA12 CA14 CA18 CA19 CA36 CA38 CC02 CD02 4J029 AA07 AB02 AC02 AD01 AE18 BA10 BB13A04 BA05 BA13 BA04 BA03 BA03 BA04 BA03 BA13 BA04 BH02 CA02 CA04 CA06 CB05A CB06A CC05A CE01 CG06 DA07 DB13 FA06 FC03 FC04 FC05 FC08 FC35 FC36 GA13 GA14 GA15 GA17 GA30 GA93 JA101 JE162 JE182 JF181 JF371 JF541 JF571

Claims (17)

[Claims] 1. At least one of the group consisting of an acid imide alcohol residue, an alkyl alcohol residue having one or more phenyl groups, and a dicyclopentadienyl and / or oligocyclopentadienyl residue as a molecular terminal group. Unsaturated polyesters containing two residues. 2. At least two residues are selected from the group consisting of acid imide alcohol residues, alkyl alcohol residues having one or more phenyl groups, and dicyclopentadienyl and / or oligocyclopentadienyl residues. The unsaturated polyester according to claim 1, wherein the most contained residue is 90 mol% or less of the molecular end groups. 3. An unsaturated polyester containing at least (a) an acid imide alcohol residue and an alkyl alcohol residue having one or more phenyl groups as a molecular terminal group,
(B) Unsaturated polyester containing acid imide alcohol residue, dicyclopentadienyl and / or oligocyclopentadienyl residue, or (c) alkyl alcohol residue having one or more phenyl groups, dicyclopenta An unsaturated polyester containing two residues of a dienyl and / or oligocyclopentadienyl residue, wherein these residues are ester-bonded with a carboxyl group at the molecular end. Saturated polyester. 4. A polypropylene glycol and / or bisphenol A, wherein the central portion of the molecular chain is mainly
At least one polyhydric alcohol residue selected from propylene oxide adducts of the group consisting of bisphenol AD, bisphenol F and bisphenol S, or a polyester chain comprising the polyhydric alcohol residue and a polycarboxylic acid residue. And a residue of at least two of the group consisting of an acid imide alcohol residue, an alkyl alcohol residue having one or more phenyl groups and a dicyclopentadienyl and / or oligocyclopentadienyl residue as a terminal group of the molecule. The unsaturated polyester according to any one of claims 1 to 3, which has a polystyrene-equivalent number average molecular weight of 600 to 3,000 and a weight average molecular weight of 800 to 5,000 in which a group is bonded. 5. The polyhydric alcohol component has a molecular weight of 190.
.About.2000 polypropylene glycol and / or at least one selected from the group consisting of propylene oxide adducts of bisphenols consisting of bisphenol A, bisphenol AD, bisphenol F and bisphenol S having a molecular weight of 650 to 2000. 4. The soft unsaturated polyester according to any one of 4 above. 6. An unsaturated polycarboxylic acid monoester residue occupying the terminal of an unsaturated polyester (UPE) [an alkyl dicarboxylic acid residue having one carboxyl group and an acid imide alcohol residue, or an alkyl having at least one phenyl group] Occupancy (FF) of monoester monocarboxylic acid residue in which at least two of alcohol residue and dicyclopentadienyl and / or oligocyclopentadienyl residue are half-ester bonded (MMC residue) , FF = [(number of moles of MMC residue) / (number of moles of UPE) ×
2)] × 100 (however, the number of moles of MMC residue = the number of moles of monoester monocarboxylic acid, and the number of moles of UPE = the total weight of UPE / the number average molecular weight is calculated). The unsaturated polyester according to claim 1, wherein the occupancy of the unsaturated polycarboxylic acid monoester residue in the polyester terminal is 60% or more. 7. At least two mono groups selected from the group consisting of (A) an acid imide alcohol component, an alkyl alcohol component having one or more phenyl groups and a dicyclopentadienyl and / or oligocyclopentadienyl residue-containing component. An alcohol component, (B) a polyhydric alcohol component,
A process for producing an unsaturated polyester, which comprises reacting an unsaturated polycarboxylic acid component (C) or a saturated polycarboxylic acid component (D) with the unsaturated polycarboxylic acid component. 8. At least 2 of the group consisting of an unsaturated dicarboxylic acid and an acid imide alcohol component, an alkyl alcohol component having one or more phenyl groups and a dicyclopentadienyl and / or oligocyclopentadienyl residue-containing component. The method for producing an unsaturated polyester according to claim 7, wherein a monoester monocarboxylic acid mixture obtained by reacting two monoalcohol components is used. 9. At least two mono groups selected from the group consisting of (A) an acid imide alcohol component, an alkyl alcohol component having one or more phenyl groups and a dicyclopentadienyl and / or oligocyclopentadienyl residue-containing component. 50 parts by weight of an alcohol component and (B) at least one selected from polypropylene glycol, bisphenol A, bisphenol AD, bisphenol F and bisphenol S adduct of propylene oxide in 100 parts by weight of a polyhydric alcohol component. Part or more of the polyhydric alcohol component and the unsaturated carboxylic acid component which is at least one selected from (C) unsaturated polyhydric carboxylic acid and its reactive derivative are subjected to an esterification reaction, or with these At the same time, (D) saturated polycarboxylic acid, aromatic polycarboxylic acid An ester having a saturated polycarboxylic acid component which is at least one selected from a carboxylic acid and a reactive derivative thereof, and an ester having an acid imide alcohol residue and at least one phenyl group as an end group; A polystyrene-reduced number average molecular weight of 600 to 3,000 and a weight average molecular weight of 800 to are obtained by binding at least two residues of the group consisting of an alcohol residue and a dicyclopentadienyl and / or oligocyclopentadienyl residue. A method for producing a soft unsaturated polyester, which comprises producing 5,000 polyesters. 10. (C) Unsaturated polycarboxylic acid and (D)
The ratio of the saturated polycarboxylic acid is (D) / (C) = 0
The method for producing a soft unsaturated polyester according to claim 7, wherein the ratio is 4.00. 11. An unsaturated compound prepared by adding 5 to 55 parts by weight of a copolymerizable radically polymerizable monomer to 100 parts by weight of the unsaturated polyester according to any one of claims 1 to 6. Polyester resin. 12. An FRP waterproof material comprising 100 parts by weight of the unsaturated polyester resin according to claim 11 and 15 to 80 parts by weight of a fiber reinforcing material. 13. The method according to claim 12, with respect to the pretreated substrate.
A method for applying an FRP waterproof material, comprising applying and curing the FRP waterproof material according to 1. 14. A resin mortar lining material obtained by mixing 100 to 500 parts by weight of a filler and / or an aggregate with the unsaturated polyester resin according to claim 11. 15. The method according to claim 14 with respect to the pretreated substrate.
A method for applying a cured resin mortar lining, which comprises applying and curing the resin mortar lining material as described in 1. 16. The filler / aggregate 300 to 13 relative to 100 parts by weight of the unsaturated polyester resin according to claim 11.
A resin concrete composition containing 100 parts by weight. 17. A curing agent and a filler / aggregate 3 relative to 100 parts by weight of the unsaturated polyester resin according to claim 11.
A resin concrete molded product obtained by mixing and curing 0 to 1300 parts by weight.