JP3435841B2 - Resin concrete composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin concrete composition.
For products, more specifically, dispersion stability and low
The present invention relates to a resin concrete composition having excellent shrinkability. [0002] Unsaturated polystyrene is used in place of Portland cement.
Using curable resin such as polyester resin as binder,
Add mineral filler such as calcium carbonate or sand, gravel
Resin concrete mixed with aggregate mainly composed of
Is water and acid resistant compared to cement based concrete
Excellent in properties, chemical resistance, electrical insulation and curability, and lighter
Because of the volume and strength, manholes and road signs
It is widely used for civil engineering and building materials. Ma
In recent years, it is located between sewage and agricultural water pipes and cable protection pipes.
It is also used as a material for forming layers, and its required properties are
It is growing. [0003] However, as a binder for resin concrete,
Unsaturated polyester resin is generally 6 to 10 at the time of curing.
% Shrinkage, resulting in cracks and distortion in molded products.
Or lacks dimensional accuracy.
You. [0004] In order to improve these problems, unsaturated
Various thermoplastic resins are used as low shrinkage agents in polyester resin.
There has been proposed a method of compounding by mixing. Among thermoplastic resins
Even polystyrene is the most commonly used because it is inexpensive
However, the compatibility with the unsaturated polyester resin is low,
In the curing process, the surface of the molded product
Of stickiness and mold stains at
There was a problem that workability deteriorated. Therefore, the present inventors have disclosed Japanese Patent Application Laid-Open No. 60-991.
No. 15, the unsaturated polyester of polystyrene
Into polystyrene to improve compatibility with
Polymer part containing vinyl acetate as a structural unit as a dispersion stabilizer
And a polymer portion having styrene as a structural unit.
A method using rock copolymer together was proposed. Also, JP
Japanese Unexamined Patent Publication No. 57-80413 discloses an unsaturated polyester resin.
Vinyl acetate, which has excellent compatibility with polyester resin, as a structural unit
A polymer portion, and a polymer portion having styrene as a structural unit.
Formulating a block copolymer consisting of
Proposed the law. However, these block copolymers
Is commonly used for cold molding of resin concrete compositions.
Low reactivity unsaturated polyester resin and low shrinkage agent used
Compatibility is too high and phase separation does not occur during curing
Therefore, it had no effect as a low shrinkage agent. Further, the present inventors have found that low shrinkage for room temperature molding is possible.
As an agent, JP-B-63-30956, JP-B-63-30956
-40447, JP-B-4-7390 and JP-B-4-7390.
In Japanese Patent Publication No. Hei 4-7391, acrylic acid or
Polymer containing alkyl ester of tacrylic acid as a constitutional unit
Part and a polymer part having styrene as a constitutional unit.
Block copolymer was proposed. In addition, JP-A-4-3
No. 11761, vinyl acetate and crotonic acid, etc.
A non-conjugated ethylenically unsaturated carboxylic acid as a structural unit
Part and a polymer part having styrene as a constitutional unit
A block copolymer consisting of [0008] However, the former low-shrinkage agent is polystyrene.
Low compatibility with unsaturated polyester resin
And had various problems related to this. The latter low yield
The condensing agent also constitutes vinyl acetate in the low-contracting agent.
Resin polymer is too large
Low repellency commonly used in cold forming of concrete compositions
Works effectively for responsive unsaturated polyester resins.
Did not. SUMMARY OF THE INVENTION As described above,
Since then, it has been commonly used for cold molding of resin concrete compositions.
For the low-reactivity unsaturated polyester resin used,
Excellent low shrinkage agent in both compatibility and low shrinkage
do not do. Therefore, with satisfactory dimensional accuracy and surface properties
It was difficult to obtain resin concrete. The present invention addresses these problems of the prior art.
It was done with your eyes. The purpose is to
Resin control with excellent dispersion stability and low shrinkage during room temperature molding
It is to provide a cleat composition. [0011] The present inventors have achieved the above object.
As a result of intensive studies to achieve the present invention, the present invention has been completed.
That is, the resin concrete composition of the present invention has a low yield.
Polymer part A having vinyl acetate as a structural unit as a condensing agent
And a polymer part B having styrene as a constitutional unit.
-The B-type block copolymer and polystyrene in total
Total weight of unsaturated polyester and ethylenically unsaturated monomer
3 to 18 parts by weight per 100 parts by weight of the above-mentioned A-
When the proportion of the polymer portion A in the B-type block copolymer is 2 to 5
0% by weight, and the proportion of the polymer part B is 98 to 50% by weight.
And vinyl acetate in the low-shrinkage agent as a structural unit.
Having a polymer portion ratio of 0.01 to 0.19% by weight
It is. In addition, the resin concrete composition in the present invention
The thing contains a resin mortar composition. Hereinafter, the present invention will be described in detail.
The unsaturated polyester in the present invention is an α, β-unsaturated polyester.
Dibasic acid or its anhydride and saturated dibasic acid or its
Using a mixture of water and a polyhydric alcohol in the usual manner
Unsaturated polyester obtained by polycondensation
You. The composition ratio of each component is not particularly limited.
From reactive unsaturated polyesters to highly reactive unsaturated polyesters
You can use any of them up to a stele,
In cold forming of concrete compositions, α, β-unsaturated disalts
15-50 mol% of base acid or its anhydride and saturated dibasic acid
Or a mixture thereof with 85 to 50 mol% of anhydride and polyhydric alcohol.
Low-reactivity unsaturated polyester produced from alcohol
Is preferably used. The above α, β-unsaturated dibasic acid or its non-
The hydrates include, for example, maleic acid or its anhydride,
Malic acid, mesaconic acid, tetraconic acid, itaconic acid
Can include these alkyl esters and the like.
As the saturated dibasic acid or its anhydride, for example, anhydrous
Phthalic acid, orthophthalic acid, isophthalic acid, terephthalic acid
Acid, tetrahydrophthalic acid, halogenated phthalic anhydride,
Adipic acid, sebacic acid, heptic acid, succinic acid or
These alkyl esters can be exemplified. Ma
Examples of the polyhydric alcohol include ethylene glycol.
Coal, diethylene glycol, triethylene glycol
Propylene glycol, dipropylene glycol,
Butylene glycol, neopentyl glycol, 1,3
-Butanediol, 1,4-butanediol, 1,6-
Dimers such as hexanediol and cyclohexanedimethanol
Oars, hydrogenated bisphenol A, bisphenol A
Other than glycols such as propylene oxide,
Examples include triols such as trimethylolpropane.
I can do it. The unsaturated polyester according to the present invention is
Examples of copolymerizable ethylenically unsaturated monomers include styrene
, Vinyltoluene, α-methylstyrene, t-butyl
Styrene derivatives such as styrene and chlorostyrene;
Alkyl or methacrylic acid esters, vinyl acetate
One or two of these groups.
Although selected from the above, styrene is particularly preferred. [0015] The unsaturated polyester and the ethylenically unsaturated
The preferred usage ratio of the sum monomer is 30/70 to 70/3.
0% by weight. Less than 30% by weight of unsaturated polyester
When the ethylenically unsaturated monomer exceeds 70% by weight
Low strength of the resulting resin concrete
70% by weight of unsaturated polyester
When the content exceeds 30% by weight of the ethylenically unsaturated monomer
The viscosity of the resulting resin concrete composition
This tends to increase the workability and the workability. The low-shrinkage agent in the present invention is vinyl acetate.
The polymer part A as a structural unit and styrene as a structural unit
AB block copolymer comprising a polymer portion B
And polystyrene, which is acetic acid
The ratio of the polymer part having vinyl as a constitutional unit is 0.01 to
0.19% by weight is an essential requirement
You. Weight of vinyl acetate as a constituent unit in low shrinkage agent
If the ratio of the united portion is less than 0.01% by weight, low yield
Low compatibility between condensing agent and unsaturated polyester resin, low yield
Since the condensing agent emerges on the surface during the curing process, it
And the workability tends to deteriorate.
If it exceeds 0.19% by weight, resin concrete
Low reactivity unsaturation commonly used in cold forming of compositions
The compatibility between the Japanese polyester resin and the low-shrinkage agent increases,
As a low shrinkage agent, phase separation does not occur during curing
Does not work. A polymer having vinyl acetate as a structural unit
From part A and polymer part B having styrene as a constitutional unit
AB block copolymer and polystyrene in combination
The ratio is based on vinyl acetate in the low shrinkage agent as a constituent unit.
Is determined so that the proportion of the polymer portion falls within the above range.
You. As a polystyrene, general-purpose grade, high
Use commercially available products such as flow grades and impact grades.
Can be used, but preferably the average molecular weight is
Gel permeation chromatography
Styrene-equivalent number average molecular weight of 10,000 to 300,
000, and more preferably 30,000-20.
It is 0000. If less than 10,000
Molding shrinkage of the resin concrete composition obtained from
It becomes large and cracks easily occur. 300,0
If the value exceeds 00, the resin conc
The viscosity of the reed composition increases and the workability tends to deteriorate
It is in. Also, a polymer containing vinyl acetate as a structural unit
From part A and polymer part B having styrene as a constitutional unit
In the AB type block copolymer, the polymer portion A
Is 2 to 50% by weight, preferably 5 to 30% by weight.
And the proportion of the polymer part B is 98 to 50% by weight, preferably
Or 95 to 70% by weight. When the proportion of the polymer portion A is 2
When the amount is less than the weight%, the content of the AB type block copolymer
Extremely high proportion of polymer portion A containing vinyl acetate as a structural unit
As a dispersion stabilizer for block copolymers
Effect is low, resulting in low shrinkage and unsaturated polyester
Low compatibility with telluric resin, low shrinkage agent
To stick out on the molded product surface,
Workability tends to deteriorate. The proportion of the polymer part A exceeds 50% by weight
In this case, vinyl acetate occupying the low shrinkage agent
Of the polymer portion to be 0.01 to 0.19% by weight.
AB block copolymer blended to make
Is extremely low, resulting in low
Low compatibility with Japanese polyester resin, cures low shrinkage agent
Adhesive on the surface of the molded product because it emerges on the surface during the process
And workability tends to deteriorate. In the present invention, vinyl acetate occupying in the low shrinkage agent is used.
The proportion of the polymer portion having a structural unit of
Should be set to. Therefore, AB type block copolymer
The proportion of the polymer part A in the low shrinkage agent
Increase the proportion of the block copolymer, relatively polystyrene
May be reduced. The AB type block copolymer is polymerized
Polymeric peroxide (JP-A-53-1
No. 49918)).
(Described in Japanese Patent Publication No. 60-3327), bulk polymerization method, suspension
Easy by any polymerization method such as suspension polymerization method or emulsion polymerization method
The suspension polymerization method is industrially the most suitable.
Is also preferred. At this time, the first-stage polymerization reaction of vinyl acetate
The resulting polymer having a peroxy bond in the molecule is
Removed from the reaction system as an intercalator
It can be used as a raw material, or it can be pulled without removing it from the reaction system.
Subsequently, block copolymerization can also be performed. As the polymeric peroxide, for example,
For example, those represented by the following chemical formulas (1) and (2)
Can be selected from one or more of these groups
used. Embedded image Embedded image The amount of polymeric peroxide used is vinegar
0.1 to 10 parts by weight per 100 parts by weight of vinyl acid
Preferably. Also, the polymerization temperature is
40-80 ° C for the second stage polymerization reaction
-100 ° C., and the polymerization temperature in the second-stage polymerization reaction
The temperature is preferably higher than the polymerization temperature in the first-stage polymerization reaction.
Good. The polymerization time is 1 to 3 hours in the first stage polymerization reaction,
In the two-stage polymerization reaction, the reaction is preferably performed for 3 to 10 hours. By the way, production of AB type block copolymer
A homopolymer of vinyl acetate and styrene is by-produced during production
However, according to the production method, net A
-The proportion of the B-type block copolymer, that is, the block rate is
Since it is as high as 80% or more, the unsaturated polyester in the present invention
Especially when used as a low shrinkage agent for terresin,
It can be used as it is without having to do it. Therefore, the book
In the AB type block copolymer of the present invention, vinyl acetate is used.
The polymer portion A having phenyl as a constitutional unit is a vinyl acetate
The polymer portion B having styrene as a structural unit is
It shall include a homopolymer of len respectively. The amount of the low shrinkage agent is determined by the amount of the unsaturated polystyrene.
To 100 parts by weight of the total weight of
3 to 18 parts by weight, preferably 6 to 14 parts by weight
Department. When less than 3 parts by weight, it is obtained from this
The molding shrinkage of the resin concrete composition increases,
Cracks are likely to occur. When exceeding 18 parts by weight
The viscosity of the resulting resin concrete composition
This tends to increase the workability and the workability. As the curing agent in the present invention, for example,
Ton peroxide, diacyl peroxide, peroxy
Esters, peroxyketals, hydroperoxides,
Of unsaturated polyester resin such as dialkyl peroxide
Known curing catalysts used for curing can be mentioned,
Depending on the desired molding temperature and molding time, one of these groups
Alternatively, two or more are selected. Especially in cold forming
Is organic such as cobalt naphthenate, cobalt octenoate
Metals, N, N-dimethylaniline, N-ethylmethato
Aromatic or fat, such as luisin and triethanolamine
Aromatic amines, β-diketones such as acetylacetone, etc.
In general, a curing accelerator is used in combination with the curing agent.
As the most common combination of curing agent and curing accelerator
Is methyl ethyl ketone peroxide / naphthenic acid
Benzoyl peroxide / N, N-dimethylani
Phosphorus can be mentioned. Therefore, the curing agent of the present invention also contains a curing accelerator.
Shall be included. The amount of the curing agent excluding the curing accelerator is
Although not limited to, preferably unsaturated polyester and ethyl
100 parts by weight of total weight of lene unsaturated monomer and low shrinkage agent
0.5 to 3 parts by weight with respect to Less than 0.5 parts by weight
In some cases, the resulting resin concrete composition
Curing speed is low and productivity is poor. Over 3 parts by weight
Use hardening agent wastefully,
Sex is lost. The curing accelerator is suitable for the molding conditions.
However, especially in the case of room temperature molding,
Is preferably an unsaturated polyester and an ethylenically unsaturated monomer
0.05 with respect to 100 parts by weight of the total weight of the body and the low contraction agent
１1 part by weight. If less than 0.05 parts by weight,
Since the effect of promoting
The curing speed of concrete composition is slow and productivity is poor.
Become. If it exceeds 1 part by weight, waste the curing accelerator
Use, and the economics are lost. As the filler in the present invention, calcium carbonate
Cium, glass powder, aluminum hydroxide, talc,
Inorganic fine powder such as leh, kaolin, stone powder, wood powder, sand, sand
Inorganic particulate matter such as crushed stone, crushed stone, quartzite, and cold water stone
Can be selected from one or more of these groups
You. The amount of the filler is not particularly limited, but is preferably
Unsaturated polyester, ethylenically unsaturated monomer and low shrinkage agent
30 to 1000 weight per 100 weight parts of total weight
Parts, more preferably 50 to 800 parts by weight. 30
If the amount is less than 10 parts by weight, the resin resin
The shrinkage of the molding composition increases, and cracks occur.
It is easy to live and loses economic efficiency. 1000 parts by weight
If it exceeds, the resin concrete obtained from this
The strength of the metal tends to decrease and the material tends to become brittle. Further, the resin concrete composition of the present invention
Products, generally used in unsaturated polyester resin compositions
Inhibitor, curing regulator, thickener, internal release
It is possible to mix appropriate amounts of agents, coloring agents, and reinforcing materials as needed.
it can. Inhibitors include hydroquinone, 1,4-
Quinones such as nzoquinone, 4-t-butylcatechol and the like
Catechols, as a curing regulator, ascorbin
Acid and α-methylstyrene dimer, as a thickener,
Magnesium oxide, calcium oxide, magnesium hydroxide
And oxides of alkaline earth metals such as calcium hydroxide
Or hydroxide, as the internal release agent, stearic acid,
Colors zinc stearate, calcium stearate, etc.
As an agent, an organic dye or an inorganic pigment is used as a reinforcing material.
Is inorganic fiber such as glass fiber and carbon fiber, aramid fiber,
Organic fibers such as polyester fibers can be mentioned. The resin concrete composition of the present invention comprises:
Generally, after casting into molds, resin molds, wood molds, etc., 10-40 ° C
At room temperature. Further, the resin of the present invention
Concrete compositions are moderately reactive or highly reactive unsaturated
Molding temperature of 40-150 ° C using polyester resin
It can also be applied in the field of
Compression molding of resin concrete moldings such as metal lids
It can also be manufactured by a method. Furthermore, the present invention
Resin concrete composition for sewage and agricultural water pipes and cables
When used as a material for the intermediate layer of a protective tube
Means filament winding or centrifugal molding
Is also used. The constituents of the resin concrete composition of the present invention
Some low-shrinkage agents are compatible with unsaturated polyester resins.
Highly soluble vinyl acetate polymer unit
include. For this reason, unsaturated polyester resin
Good dispersion stability of resin concrete composition as mix
It is good. In addition, vinyl acetate in the low shrinkage agent
The ratio of the polymer part to be the constituent unit is the minimum required.
Commonly used for cold molding of resin concrete compositions.
Low reactivity unsaturated polyester resin and low shrinkage agent used
Compatibility is too high and no phase separation occurs during curing
The problem that it does not work effectively as a low shrinkage agent
Never. Therefore, it has excellent low shrinkage during normal temperature molding.
A resin concrete composition can be obtained. The present invention will now be described with reference to Examples, Examples and Comparative Examples.
This will be described more specifically. Note that in these examples
Parts and percentages are by weight unless otherwise indicated.
It represents% by weight. In addition, the measurement items in each example are as follows.
So we did. (1) Polymer obtained by production of block ratio AB type block copolymer
Part of the mixture was initially extracted with cyclohexene using a Soxhlet extractor.
24 hours using sun as eluent, then methanol
The liquid was extracted for 24 hours. By cyclohexane extraction
The amount of weight loss is indicated by polystyrene (hereinafter abbreviated as PS),
The weight loss due to the ethanol extraction was calculated as polyvinyl acetate (hereinafter
PVAc) (abbreviated as PVAc).
The content was taken as the content of the AB block copolymer. And heavy
Ratio of net AB block copolymer in the compound
Is the block rate. (2) Polymer portion A in AB type block copolymer and weight
Polymer Obtained by Production of AB Block Copolymer Constituent Ratio with Merged Part B
Nuclear magnetic resonance spectroscopy was performed using part of
(Hereinafter abbreviated as VAc).
Area of signal (chemical shift δ = about 5.2 ppm), immediately
The integral value and benzene of styrene (hereinafter abbreviated as St)
A signal corresponding to a ring proton (chemical shift δ = about 6.
4 to 7.1 ppm), that is, A
-Weight of VAc in B-type block copolymer as a constitutional unit
The structure of the united portion A and the polymer portion B having St as a constituent unit.
The composition ratio (hereinafter abbreviated as A / B) was determined. (3) Polymerization with VAc as a constituent unit in low shrinkage agent
According to the following formula, VAc occupying in the low contraction agent is defined as a structural unit.
Ratio of polymer portion (hereinafter abbreviated as ratio of PVAc portion)
). The ratio (%) of the PVAc portion = (AB type)
Amount of lock copolymer × Ratio of polymer part A) / (P
Compounding amount of S + compounding amount of AB block copolymer) x 1
00 (4) Linear shrinkage ratio 140 mm inner diameter and 1 outer diameter on a glass plate treated with a release agent.
Install a 70 mm, 30 mm high stainless steel ring.
Various resin concrete or resin mortar composition
Inject material and cure in 25 ° C constant temperature bath, 1 day after curing
The molded product was released from the mold, and the linear shrinkage was measured by the following equation. Linear shrinkage (%) = [(Stainless steel ring
Inner diameter)-(outer diameter of molded product)] / (of stainless steel ring)
Inner diameter) × 100 (5) Surface of resin concrete or resin mortar
Condition Various resin concrete or resin mortar molded products
In addition to observing the surface condition of the surface,
The presence or absence of tackiness was examined according to the following criteria. ：: good, no prominence of low shrinkage agent on surface
Show good condition. ×: Adhesion due to embossing of low shrinkage agent on surface is observed
Indicates a bad state. (6) Surface gloss of molded article JIS-K-7105 (Optical property test of plastic
Method), a gloss meter manufactured by Toyo Seiki Seisaku-sho, Ltd.
Various resin concrete or resin moles
Surface gloss on the glass side of the molded product (60 ° mirror gloss)
Degree) was measured. [Production of AB type block copolymer of the present invention] (Reference Example 1) Thermometer, nitrogen inlet tube, stirrer, and condensate
300 parts of water in a glass reactor equipped with
Rivinyl alcohol (Nippon Synthetic Chemical Industry Co., Ltd., product
Name: 15 parts of 1% aqueous solution of Gohsenol KH-17) and
10% aqueous dispersion of hydroxyapatite (Nippon Chemical
Made by Sangyo Co., Ltd., trade name: Super Tight 10) 15 parts
I was crowded. Next, the polymeric paint represented by the above formula (1)
Oxide (hereinafter abbreviated as P.PO) 0.5 part
After dispersing in an aqueous solution at room temperature for 1 hour, 10 parts of VAc was prepared.
At 60 ° C. with stirring while introducing nitrogen into the reactor.
Polymerization (first-stage polymerization reaction) was performed for 2 hours. Thereafter, the mixture was cooled to room temperature, and St9 was added to the reactor.
0 parts were charged and impregnated at room temperature for 1 hour with stirring.
Thereafter, while introducing nitrogen into the reactor, the mixture was stirred at 80 ° C. for 8 hours.
Time, followed by polymerization at 90 ° C for 30 minutes (second stage polymerization reaction)
Was done. After cooling to room temperature, the obtained polymer was
Wash with 130 parts of hydrochloric acid, then with water, filter off and dry in vacuo
94 parts of a white granular polymer were obtained. Part of the obtained polymer
Is used to determine the block ratio and the AB type block copolymer.
A / B was determined. The results are shown in Table 1. (Reference Examples 2 and 3) P / PO, VAc and St Charges
Were the same as in Reference Example 1 except that was changed as shown in Table 1.
To produce an AB block copolymer, and a white granular
A polymer was obtained. Using a portion of the polymer obtained, block
And the A / B in the AB block copolymer were determined.
The results are shown in Table 1. [Production of AB type block copolymer outside the present invention] (Reference Examples 4 and 5) Charged amounts of P • PO, VAc and St
Were the same as in Reference Example 1 except that was changed as shown in Table 1.
To produce an AB block copolymer, and a white granular
A polymer was obtained. Using a portion of the polymer obtained, block
And the A / B in the AB block copolymer were determined.
The results are shown in Table 1. The AB type tubes obtained in Reference Examples 1 to 5 were used.
Each of the lock copolymers has a solid content of 30%.
Diluted with St, and provided to each example as a St dispersion.
Was. [Table 1] [Preparation of St Solution of PS] (Reference Example 6) PS (trade name: Diamond, manufactured by Mitsubishi Kasei Corporation)
Rex HF77, number average molecular weight: about 80,000)
Dilute with St so as to have a solid content of 30%, and stabilize PS
The solution was used. [Comparative Low Shrinkage Agent] (Reference Example 7) Modiper MS10B manufactured by NOF Corporation
-30 (polymer part having methyl methacrylate as a constitutional unit)
And a polymer portion having St as a structural unit.
(St dispersion of solid copolymer, solid content 30%)
It was used as a contracting agent (A). (Reference Example 8) Modiper S101- manufactured by NOF Corporation
30 (polymer part containing VAc and crotonic acid as constituent units)
Consisting of and a polymer portion having St as a structural unit
Low dispersion for comparison (St dispersion of copolymer, solid content 30%)
Agent (B). [Production of unsaturated polyester resin] (Reference Example 9) 0.13 mol of fumaric acid, orthophthalic acid
0.36 mol, 0.36 mol of propylene glycol and
Known method using 0.15 mol of diethylene glycol
The unsaturated polyester alkyd obtained by polycondensation with
Diluted to make the solid content 61%, low reaction
(26.5 mol% reactivity) unsaturated polyester resin
Was manufactured. [Preparation of resin concrete composition and preparation of molded article] (Example 1) Unsaturated polyester tree obtained in Reference Example 9
70 parts of fat, 29.8 St solution of PS obtained in Reference Example 6
5 parts and AB type block copolymer obtained in Reference Example 1
After mixing 0.15 parts of St dispersion liquid for 5 minutes with a stirrer,
Nippon Yushi Co., Ltd.'s Permec N (methyl ethyl ketone
Trade name of 55% dimethyl phthalate solution of peroxide
And 0.4 part of a 6% St solution of cobalt naphthenate
And further mixed. Then there is calcium carbonate 10
0 parts and 300 parts of river sand (maximum particle size 5 mm)
A concrete composition was obtained. This composition is treated with a release agent
140 mm inside diameter, 17 outside diameter installed on a glass plate with
Injected into a 0 mm, 30 mm high stainless steel ring, 2
Cure in a 5 ° C constant temperature bath, remove the molded product one day after curing
did. Observing the surface condition of the upper surface of the molded product
Then, the presence or absence of surface tackiness was examined by a finger test. Ma
The linear shrinkage of the molded product and the surface gloss of the glass side were measured.
Was. The results are shown in Table 2. (Examples 2 to 7) In Example 1, obtained in Reference Example 9
Unsaturated polyester resin, of the PS obtained in Reference Example 6.
St solution and AB type blocks obtained in Reference Examples 1 to 3
Except that St dispersion of the copolymer is used as shown in Table 2.
Prepares a resin concrete composition according to Example 1.
Then, a molded product was produced. The results are shown in Tables 2 and 3. [Table 2] [Table 3] As shown in Tables 2 and 3, Examples 1 to
The resin concrete composition of No. 7 has a molded product surface
The surface condition is good and the low shrinkage
Low shrinkage and excellent surface gloss. (Comparative Examples 1 to 6) Obtained in Reference Example 9 in Example 1.
Unsaturated polyester resin, of the PS obtained in Reference Example 6.
St solution and obtained in Reference Example 1 or Reference Examples 4 and 5.
Table 3 shows the St dispersion of the AB block copolymer.
Resin concrete according to Example 1 except that
And a molded product was prepared. The results are shown in Table 4 and
The results are shown in Table 5. Comparative Examples 1 and 2 accounted for the low shrinkage agent.
The ratio of the PVAc portion was such that Comparative Examples 3 and 4 were blended AB
The ratio of the polymer part A in the mold block copolymer is comparative example
5 and 6 indicate that the total blending amount of the low-shrinkage agent is within the scope of the claims.
It is a deviation. [Table 4] [Table 5] Incidentally, in Comparative Example 6 in Table 5, the viscosity was high,
Workability was poor. As shown in Tables 4 and 5, low yield
Polymer portion containing vinyl acetate as a constituent unit in the condensing agent
Is too small (Comparative Example 1), especially the
Surface condition is bad. Conversely, polymerization using vinyl acetate as a structural unit
When the proportion of the body part is excessive (Comparative Example 2), the contraction rate is
Large, poor surface gloss. AB block copolymer
When the proportion of the polymer portion A is too small or too large (Comparative Example
3, 4), especially, the surface condition of the molded product is poor. In addition, low yield
If the compounding ratio of the condensing agent is too small (Comparative Example 5),
High shrinkage and poor surface gloss. Conversely, blending of low shrinkage agent
When the proportion is excessive (Comparative Example 6), the viscosity of the composition is high,
Poor workability. (Comparative Example 7) In Example 1, a reference example was used as a low shrinkage agent.
Of St dispersion of AB type block copolymer obtained in 1
Resin concrete according to Example 1 except that only 30 parts are used.
A reed composition was prepared and a molded article was prepared. as a result,
The upper surface of the molded product has no stickiness due to the emergence of the low shrinkage agent,
Despite good surface condition, linear shrinkage was as large as 0.82%.
The surface gloss on the glass side is very low (15%)
Met. This comparative example is described in JP-A-57-80413.
This is a supplementary test of the gazette. (Comparative Example 8) In Example 1, a reference example was used as a low shrinkage agent.
Except using 30 parts of the comparative low-shrinkage agent (A) obtained in 7
Prepares a resin concrete composition according to Example 1.
Then, a molded product was produced. As a result, the linear shrinkage of the molded product is
As low as 0.06%, the surface gloss on the glass side is also 85%
Although it was expensive, a low shrinkage agent emerged on the upper surface of the molded product
The stickiness was found. This comparative example is shown in
This is a supplementary test of JP-A-3-30956. (Comparative Example 9) In Example 1, a reference example was used as a low shrinkage agent.
Except using 30 parts of the comparative low-shrinkage agent (B) obtained in 8
Prepares a resin concrete composition according to Example 1.
Then, a molded product was produced. As a result, the upper surface of the molded product has low shrinkage
No stickiness due to embossing of the agent, showing good surface condition
However, the linear shrinkage was as large as 0.79%,
The surface gloss was as low as 18%. The book
The comparative example is a supplementary test of Japanese Patent Application Laid-Open No. 4-311761. [Preparation of resin mortar composition and preparation of molded article] (Example 8) Unsaturated polyester resin obtained in Reference Example 9
70 parts of fat, 29.8 St solution of PS obtained in Reference Example 6
5 parts and AB type block copolymer obtained in Reference Example 1
After mixing 0.15 parts of St dispersion liquid for 5 minutes with a stirrer,
Nipper FF-K (benzoylper) manufactured by NOF Corporation
Oxide 50% dicyclohexyl phthalate diluted product
(Product name) 2 parts and 0.2 parts of N, N-dimethylaniline
And mixed. Then, there is a filler (calcium carbonate
1, silica sand No. 3 is 2, silica sand 4 is 1, and silica sand 7 is 1.
100 parts by weight) and mixed to form a resin mortar composition
I got This composition is placed on a glass plate that has been treated with a release agent.
The installed inner diameter 140mm, outer diameter 170mm, height 30mm
Inject into Tenres ring and cure in 25 ° C constant temperature bath
One day after curing, the molded product was released from the mold. And molded products
Observe the surface condition of the upper surface and display
The surface was checked for tackiness. In addition, the linear shrinkage
The surface gloss on the glass side was measured. The results are shown in Table 6.
Was. (Examples 9 to 14) In Example 8, obtained in Reference Example 9
Unsaturated polyester resin, PS obtained in Reference Example 6
Solution and the AB block obtained in Reference Examples 1-3.
Except for using a St copolymer dispersion liquid as shown in Table 4.
Prepared a resin mortar composition according to Example 1,
A molded article was produced. The results are shown in Tables 6 and 7. [Table 6] [Table 7] As shown in Tables 6 and 7, Examples 8 to
Each of the resin mortar compositions of No. 14 has a surface
Good condition, low shrinkage and excellent surface gloss
I have. (Comparative Examples 10 to 15) In Example 8, obtained in Reference Example 9
Unsaturated polyester resin, P obtained in Reference Example 6
S solution of S and obtained in Reference Example 1 or Reference Examples 4 and 5.
Table 5 shows the obtained St dispersion liquid of the AB block copolymer.
Resin mortar according to Example 1 except that
To prepare a molded product. The results are shown in Table 8 and
The results are shown in Table 9. Comparative Examples 10 and 11 were occupied by the low shrinkage agent.
Comparative Examples 12 and 13 are blended with each other.
Of polymer part A in AB type block copolymer obtained
However, in Comparative Examples 14 and 15, the total amount of the low shrinkage agent was
It is outside the scope of the claims. [Table 8] [Table 9] In Comparative Example 15 in Table 9, the viscosity was high.
And the workability was poor. As shown in Tables 8 and 9,
Polymer containing vinyl acetate as a constituent unit in low shrinkage agent
When the proportion of the portion is too small (Comparative Example 10), the molding
The surface condition of the product is poor. Conversely, vinyl acetate is a structural unit.
When the ratio of the polymer portion is too large (Comparative Example 11),
High shrinkage and poor surface gloss. AB type block
When the proportion of the polymer portion A in the polymer is too small or too large
(Comparative Examples 12 and 13), especially the surface condition of the molded product is poor.
In addition, when the blending ratio of the low shrinkage agent is too small (Comparative Example 1
4) The molded article has a large shrinkage and poor surface gloss. Reverse
In addition, when the compounding ratio of the low shrinkage agent is excessive (Comparative Example 15),
The viscosity of the composition is high and workability is poor. (Comparative Example 16) In Example 8, a reference as a low shrinkage agent
St dispersion of AB type block copolymer obtained in Example 1
Resin moles according to Example 8 except that only 30 parts were used.
A barrel composition was prepared to produce a molded article. As a result,
The top surface of the molded product has no stickiness due to the embossing of the low shrinkage agent.
Despite good surface condition, linear shrinkage was as large as 1.42%.
The surface gloss on the glass side is very low at 13%
there were. This comparative example is disclosed in JP-A-57-80413.
It is a retest of the report. (Comparative Example 17) In Example 8, a reference as a low-shrinkage agent
Using 30 parts of the comparative low-shrinkage agent (A) obtained in Example 7
Outside, a resin mortar composition was prepared according to Example 8.
Then, a molded product was produced. As a result, the linear shrinkage of the molded product is
As small as 0.08%, the surface gloss on the glass side is 91%
Although it was expensive, a low shrinkage agent emerged on the upper surface of the molded product
The stickiness was found. This comparative example is shown in
This is a supplementary test of JP-A-3-30956. (Comparative Example 18) In Example 8, a reference as a low-shrinkage agent
Using 30 parts of the comparative low-shrinkage agent (B) obtained in Example 8
Outside, a resin mortar composition was prepared according to Example 8.
Then, a molded product was produced. As a result, low yield
Good surface condition with no stickiness due to embossing of the condensing agent
However, the linear shrinkage was as large as 1.44%,
The surface side gloss was as low as 17%. What
This comparative example is based on a supplementary test of JP-A-4-311761.
is there. When comparing the above Examples and Comparative Examples, acetic acid
Constructs polymer part A with vinyl as the structural unit and styrene
AB block copolymer consisting of polymer unit B as a unit
The polymer part with vinyl acetate as a structural unit
Low-shrinkage agent containing specific proportion
Incorporating into resin concrete composition as binder
Excellent dispersion stability and low shrinkage during room temperature molding
Gin concrete composition can give
Obtain molded products with excellent dimensional accuracy and surface properties
Is clear. It should be noted that the claims ascertained from the above embodiment are
Other technical ideas are described below, together with their effects.
Put on. (1) The unsaturated polyester is an α, β-unsaturated dibasic acid
Or its anhydride as a minor component, saturated dibasic acid or
A mixture containing the anhydride as a main component, a polyhydric alcohol and
2. The method according to claim 1, which is of low reactivity produced from
Resin concrete composition. With this configuration,
Room temperature molding with gin concrete composition
Can be. (2) AB type block copolymer is subjected to a two-stage polymerization reaction
The polymerization temperature in the second stage polymerization reaction
2. The method according to claim 1, wherein the temperature is set higher than the polymerization temperature in the combined reaction.
Resin concrete composition described above. With this configuration,
Block ratio of the block copolymer can be increased.
It can also be used in resin concrete compositions. (3) The curing agent according to claim 1, wherein the curing agent is used in combination with a curing accelerator.
Resin concrete composition. With this configuration, the cash register
Can increase the curing rate of the concrete composition,
Productivity can be improved. As described in detail above, the resin of the present invention
According to the concrete composition, dispersion stability and room temperature molding
Excellent in both properties of low shrinkage, dimensions of concrete molded products
Legal accuracy can be ensured. And concrete
The surface condition of the molded article can be maintained well. Follow
Thus, the present invention is industrially useful.

────────────────────────────────────────────────── (5) Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08L 25:04) (56) References JP-A-60-99115 (JP, A) JP-A-56-79113 (JP, A) JP-A-57-80413 (JP, A) JP-A-4-311761 (JP, A) JP-B-63-30956 (JP, B2) JP-B-63-40447 (JP, B2) JP-B-4-7390 (JP, B2) JP 4-7391 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 67/06 C08F 283/01 C08F 290/00-290/14 C08F 299 / 00-299/06

Claims (1)

(57) [Claim 1] A resin comprising an unsaturated polyester, an ethylenically unsaturated monomer copolymerizable with the unsaturated polyester, a low shrinkage agent, a curing agent and a filler. In the concrete composition, as the low-shrinkage agent, an AB block copolymer composed of a polymer part A having vinyl acetate as a constitutional unit and a polymer part B having styrene as a constitutional unit, and polystyrene in total 3 to 18 parts by weight based on 100 parts by weight of the total weight of the unsaturated polyester and the ethylenically unsaturated monomer, and the ratio of the polymer part A in the AB type block copolymer is 2
-50% by weight, the proportion of the polymer part B is 98-50% by weight
And a proportion of a polymer portion having vinyl acetate as a constituent unit in the low-shrinkage agent is 0.01 to 0.19% by weight.