WO2006046602A1

WO2006046602A1 - Two-component acrylic adhesive for forming mold model and bonding method using such adhesive

Info

Publication number: WO2006046602A1
Application number: PCT/JP2005/019692
Authority: WO
Inventors: Yasuo Arai; Hidemi Doi; Tatsuro Umenoki; Kiyoyuki Noguchi; Toshitake Kanno
Original assignee: Cemedine Co., Ltd.; Okura Industrial Co., Ltd.; Kaneka Corporation
Priority date: 2004-10-26
Filing date: 2005-10-26
Publication date: 2006-05-04
Also published as: JP2006124414A; JP4681850B2; CN101052693B; CN101052693A

Abstract

Disclosed is a two-component acrylic adhesive containing a polymerizable monomer (A), an organic peroxide (B), a vanadium compound (C) and an acidic phosphate compound (D). Not less than 80 % by mass of the component (A) is composed of a (meth)acrylate having a specific molecular structure and a specific molecular weight.

Description

Vertical model manufacturing action Two-component acrylic adhesive and bonding method using the adhesive

Technical field

[0001] The present invention relates to an acrylic adhesive using a polystyrene-based resin foam as an adherend.

More specifically, the present invention relates to an adhesive used for producing a disappearance model for fabrication made of polystyrene-based resin foam.

Moreover, this invention relates to the method of manufacturing the vanishing model for forging using this adhesive agent. Background art

[0002] As a forging method for producing a porcelain, a wooden mold method, a disappearance model forging method (also called a full mold forging method or a lost form), a shrink mold method, and the like are known. In the disappearance model forging method, a disappearance model for forging made of a synthetic resin foam is prepared, and the forged mold formed by embedding the disappearance model for forging in the sand is made of molten metal (for example, molten steel). ) Pour the molten metal. By the pouring, the disappearing model for forging is burned and replaced with molten metal to produce a bowl having a shape according to the model. Since the disappearance model forging method is economical and convenient, its power in the 1960s has been rapidly spreading.

[0003] When the structure of the disappearance model for forging is complicated,

1) Produce a plurality of model parts that make up the intended vanishing model,

2) Manufactured by joining the disappeared model parts together with an adhesive.

[0004] A typical example of a synthetic resin foam that is a base material for the disappearance model for fabrication is a polystyrene-based resin foam (EPS). Disappearance for fabrication using polystyrene-based resin foam as a base material In the manufacture of models, adhesives that have been used to join model parts that comprise them include two-part epoxy, one-part urethane, and urea. Adhesives such as systems are listed.

However, since these adhesives take a long time to develop an adhesive strength with a slow curing speed, it is necessary to leave the joint to stand before moving to the next step.

Sarakuko, a two-part epoxy adhesive, is cured by an addition polymerization reaction. Mixing is essential, and in the case of poor mixing, there was a disadvantage that the adhesive strength was not improved. One-component urethane adhesives and urea adhesives cure more slowly than epoxy adhesives, and have slightly lower adhesive strength.

[0005] In addition, these adhesives have the disadvantage that many combustion residues remain when burned. If there are many combustion residues in the adhesive used in the manufacture of the disappearance model for forging, when the porcelain is manufactured using the disappearance model for forging, the combustion residue enters the interior of the object or adheres to the surface. Cheap. If the combustion residue enters the inside of the porridge or adheres to the surface, the strength of the porcelain is reduced or the workability is deteriorated. Therefore, the generation of this combustion residue has been a problem especially when manufacturing high-precision products such as automobile and ship engines and precision machine tools.

Disclosure of the invention

[0006] The inventors of the present invention have been concerned with some of the combustion residues of adhesives such as two-component epoxy-based, one-component urethane-based, and urea-based adhesives that have been conventionally used in the production of polystyrene foam foam-disappearing models. investigated. Specifically, a certain amount of the cured product of these adhesives was heated to 800 ° C at 20 ° C force at a heating rate of 10 ° CZmin in an argon atmosphere, and then the weight of the remaining residue was determined. The amount of combustion residue. For comparison, the amount of combustion residue of polystyrene foam was also determined in the same way.

As a result, when the combustion residue of polystyrene foam is 1.0, the combustion residue of the two-component epoxy adhesive is 9.0, the combustion residue of the one-component urethane adhesive is 5.2, and the urea adhesive The combustion residue of the adhesive was 17.9, which showed that the combustion residue of any adhesive was very large compared to the combustion residue of polystyrene foam.

[0007] Here, the amount of the combustion residue was measured as follows.

In a constant temperature and humidity room at 23 ° C and 50% RH, the cured product of each adhesive (in the case of a two-component adhesive, a cured product obtained by mixing equal parts of the two components), JIS In accordance with K7120, differential thermal analysis was performed under the following conditions, and the weight of the combustion residue was measured.

Measuring instrument: TGZDTA220 manufactured by Seiko Electronics Industry Co., Ltd.

Sample: Measured in lOmg in a 5φ platinum open sample container

Measurement temperature: 20 ~ 800 ° C, temperature rising speed = 10 ° CZmin, measured when 800 ° C is reached Finish

Anolegon Airflow: 300ml / min

[0008] The cause of the large number of combustion residues of these adhesives is that the main component of the adhesive is less combustible than carbon atoms and hydrogen atoms in the molecule, and has nitrogen atoms. Inferred. Therefore, the present inventors paid attention to a two-component acrylic adhesive mainly composed of a polymerizable (meth) acrylate which contains a large amount of oxygen atoms based on ester groups. About the hardened | cured material, the quantity of the combustion residue was measured like the above. As a result, when the combustion residue of polystyrene foam is 1.0, the combustion residue of the two-component acrylic adhesive is 1.3 to 3.5, which is compared with the previously used adhesives described above. As a result, it was found that there was significantly less combustion residue.

[0009] As described above, it has been found that the two-component acrylic adhesive is advantageous in that the amount of combustion residue generated is suppressed. It is also known that two-part acrylic adhesives are fast-curing and that good adhesion can be obtained even with rough mixing.

However, the polymerizable (meth) acrylates contained in conventional two-part acrylic adhesives have the property of dissolving polystyrene-based resin foam (hereinafter referred to as “dissolution in polystyrene-based resin foam”). Also called “sex”). Therefore, the conventional two-component acrylic adhesive dissolves the model part before it is cured when it is applied to the model part constituting it in the production of the lost model for fabrication made of polystyrene-based resin foam. As a result, it is easy to create gaps in the manufactured disappearance model for forging and to change the model dimensions. Furthermore, there is a problem that sufficient adhesive strength cannot be obtained.

[0010] In view of such a situation, the present invention is an adhesive that is suitably used for joining model parts constituting the same in the manufacture of a disappearance model for fabrication made of polystyrene-based resin foam,

1) The generation of combustion residue of the cured product has been reduced,

2) The property of dissolving polystyrene-based resin foam is weak

3) Strongly connect model parts, and

4) It is an object to provide an acrylic adhesive characterized in that model parts can be joined in a short time. Another object of the present invention is to provide a method for producing a disappearance model for forging easily and in a short time using this acrylic adhesive.

[0011] As a result of intensive research, the present inventor has found that the polymerizable (meta) (meta) is more than a two-component acrylic adhesive containing a polymerizable (meth) acrylate, an organic peroxide, and a radical generation accelerator. ) The present invention has been completed by finding that the above-mentioned problems can be solved by using a specific polymerizable (meth) acrylate as at least a part of the acrylate. That is, the present invention is as follows.

[1] comprising (A) a polymerizable monomer, (B) an organic peroxide, (C) a vanadium compound, and (D) an acidic phosphate compound, wherein (B) and (C) Is an acrylic adhesive that is stored in two parts so that they do not coexist,

80% by mass or more of the above (A) is a disappearance model for fabrication made of polystyrene-based resin foam, which is one or more (meth) acrylates in which the following group forces are also selected. Two-component acrylic adhesive for manufacturing.

(I) Alkyl (meth) acrylate with a molecular weight of 295 or more

(Mouth) Alicyclic (meth) acrylate with molecular weight of 195 or more

(C) Carboxyl group-containing (meth) acrylate with molecular weight of 140 or more

(2) Hydroxyl group-containing (meth) atalylate having a molecular weight of 115 or more

(E) Polyester with a molecular weight of 230 or more (Meth) acrylate

(F) Phenoxyalkylene oxide modified with a molecular weight of 310 or more (meth) acrylate

(H) Alkylene oxide-modified (meth) acrylate with bisphenol A or bisphenol F having a molecular weight of 60 or more

(Li) Polyalkylene glycol-modified (meth) acrylate with molecular weight of 520 or more

(Nu) (Meth) atarylate with a molecular weight of 600 or more

[2] The acrylic adhesive according to [1], wherein one of the two agents is placed on a smooth surface of a polystyrene-based resin foam in a constant temperature and humidity chamber at 23 ° C. and 50% RH. An adhesive characterized in that the depth of the depression formed in the polystyrene-based resin foam when 0.2 g of lgZcm ^{2 is} applied and the applied agent is wiped off after 10 minutes is 0.2 mm or less.

[3] The acrylic adhesive according to [1], which is hardened in a constant temperature and humidity chamber at 23 ° C; 50% RH. The adhesive is characterized in that the mass of the burned residue of the cured product (combustion condition: under argon atmosphere, 800 ° C) is 4% or less of the mass of the cured product before combustion.

[4] Loss for fabrication made of polystyrene resin foam, including the step of bonding the joint surfaces of model part 1 and model part 2 constituting the disappearance model for fabrication made of polystyrene resin foam to each other A method of manufacturing a model,

The pasting step includes

(a) applying one of the two acrylic adhesives described in [1] to the joint surface of the model part 1;

(b) applying the other of the two acrylic adhesives described in [1] to the joint surface of the model part 2, and

(c) A method including the step of bonding the joint surface of the model part 1 and the joint surface of the model part 2 together.

[5] Loss for fabrication made of polystyrene resin foam, including the step of bonding the joint surfaces of model part 1 and model part 2 constituting the disappearance model for fabrication made of polystyrene resin foam to each other A method of manufacturing a model,

The step of bonding the joint surfaces includes

(a) applying both of the two adhesives described in [1] to the joint surface of the model part 1, and

(b) A method including the step of bonding the joint surface of the model part 1 and the joint surface of the model part 2 together.

[0013] According to the present invention, there is provided an acrylic adhesive that hardly dissolves polystyrene-based resin foam and has improved curability. By using this adhesive, it is possible to create a model of disappearance for fabrication based on polystyrene-based resin foam, which is a highly accurate model of clay and has reduced smoke and combustion residues generated when burned. Can be manufactured.

Further, by using the method provided by the present invention, the disappearance model for forging can be easily produced in a short time.

BEST MODE FOR CARRYING OUT THE INVENTION

[0014] Acrylic Adhesive of the Present Invention> The acrylic adhesive of the present invention comprises a component (A) composed of a polymerizable monomer, a component (B) composed of an organic peroxide, a component (C) composed of a vanadium compound, and an acidic phosphate compound. (D) component is included as an essential component, but any other component such as a curing accelerator or a polymerization inhibitor may also be included.

[0015] The component (A) comprising the polymerizable monomer includes a polymerizable acrylate and Z or a polymerizable methacrylate (hereinafter, both are collectively referred to as "polymerizable (meth) acrylate"). . (A) One (or more) polymerizable (meth) acrylate may be contained in the component, but a combination of two or more types may be used.

[0016] The component (A) preferably has weak or substantially no property of dissolving the polystyrene-based resin foam. Therefore, 80% by mass or more of component (A), preferably 90% by mass or more, more preferably about 100% by mass force. One or more selected from the (meth) atrelates described in (i) to (nu) above It is preferable that it is a combination.

When the content is less than 80% by mass, the adhesive of the present invention containing the component (A) may dissolve the polystyrene-based resin foam, and thus the effects of the present invention may be impaired. .

[0017] Note that "(meth) acrylate selected from (meth) acrylate" described in (i) to (nu) "

(I) ~ (nu) of (meta) Atarirate that falls within any group!

That is, for example, a meta acrylate containing a hydroxyl group and a carboxyl group and having a molecular weight of 130 does not fall under (c), but falls under (2). Forces are also included in the (meta) aterate that is chosen.

[0018] As described above, it is preferable that 80% by mass or more of the component (A) is a combination of 1 or 2 or more selected from the (meth) atalylate forces described in (i) to (nu).

As “a combination of one or more selected from (meth) atarylates described in (i) to (nu)”, preferably (h) alone, (li) alone, (h) and Z or (ri ) And combinations of one or more of (c), (2) and (e).

[0019] (ii) Alkyl (meth) acrylate with a molecular weight of 295 or more

Alkyl (meth) acrylate is represented by CH = C (—R) COOX (R = H or Me).

2

(Meth) acrylic acid ester, wherein X is an alkyl group. The alkyl group X is preferably a chain (may be linear or branched!).

For example, cetyl (meth) acrylate is included.

[0020] (Mouth) Cycloaliphatic (meth) acrylate with molecular weight of 195 or more

Cycloaliphatic (meth) atalylate is represented by CH = C (—R) COOX (R = H or Me)

2

A (meth) acrylic acid ester, wherein X is an alicyclic group. Examples of the alicyclic group X include norborn derivatives. Examples of the norborn derivative include norbornyl having an alkyl group (for example, methyl group), or condensed norbornyl.

For example, isobornyl (meth) acrylate, dicyclopentyl (meth) acrylate, tricycle force (meth) acrylate and the like can be mentioned.

[0021] (c) Carboxy group-containing (meth) acrylate having a molecular weight of 140 or more

Carboxyl group-containing (meth) atalylate is CH = C (—R) COOX (R = H or M

2

The (meth) acrylic acid ester represented by e), wherein X is a group having a carboxyl group (—COOH).

Preferably, the compound represented by the following formula is mentioned.

[0022] [Chemical 1]

(In the formula, R «_K represents an elementary atom or a methyl group, and R ′ represents a carboxyl group or a group containing a carboxyl group (for example, an acyloxy group containing a strong lpoxyl group).)

[0023] For example, acrylic acid dimer, succinic acid 2- (meth) attaroyloxetyl, phthalic acid 2

-(Meth) atalylooxychetyl, hexahydrophthalic acid 2- (meth) atalylooxyethyl and the like. Among these, succinic acid 2- (meth) atari-oxyluchetyl having a molecular weight of 200 or more is preferable.

[0024] (2) Hydroxyl group-containing (meth) acrylate having a molecular weight of 115 or more

Hydroxyl group-containing (meth) atalylate is represented by CH = C (—R) COOX (R = H or Me).

2

(Meth) acrylic acid ester, wherein X is a group having a hydroxyl group (one OH). For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2- (meth) tert-yloxy cetyl 2-hydroxypropyl phthalate, glycerin Examples thereof include di (meth) acrylate and epoxy (meth) acrylate, such as 2-hydroxy 3 -phenoxypropyl (meth) acrylate.

Among them, glycerin di (meth) acrylate with a molecular weight of 200 or more, 2- (meth) ateroyloxyschetil 2 hydroxypropyl phthalate, and 2 hydroxy-3 phenoxypropyl (meth) acrylate, etc. The adhesive of the present invention is preferable because it can improve the curability and adhesiveness.

[0025] (e) Polyester (meth) acrylate with a molecular weight of 230 or more

Polyester (meth) acrylate is a product obtained by condensation reaction of one or both (preferably one) terminal hydroxyl groups of polyester with (meth) acrylic acid. Preferred examples of the polyester include poly force prolatathon (HO— [CO (CH 2) 2 O] —H).

2 5 n

For example, ω carboxypoly force prolatatatone mono (meth) acrylate. Of these, ω-carboxypoly force prolatatatone (η = 2 or more) mono (meth) acrylate or the like having a molecular weight of 300 or more is preferable because it can improve the curability and adhesiveness of the adhesive of the present invention.

[0026] (F) Phenoxyalkylene oxide-modified (meth) acrylate with a molecular weight of 310 or more Phenoxyalkylene oxide-modified (meth) acrylate is a phenoxyalkylene oxide or a phenoxy (poly) alkylene oxide. It is preferable that the terminal hydroxy group is a condensation reaction with (meth) attalic acid. Phenoxyalkylene oxide modification An arbitrary substituent (preferably an alkyl group such as a nor group or a Tamyl group) may be present on the phenol ring of the phenoxy group of the (meth) acrylate. Examples of phenoxyalkylene oxide include phenoxypolyethylene oxide.

Specific examples of (f) include substituted or unsubstituted phenoxypolyethylene oxide-modified (meth) acrylate represented by the following formula. Examples of substituted phenoxypolyethylene oxide-modified (meth) acrylates include nourphenoxypolyethylene oxide-modified (meth) acrylate, tamyl (preferably ρ-tamyl) phenoxyethylene oxide modified ( (Meth) acrylate and the like.

Among them, phenoxypolyethylene oxide (n = 4 or more) modified (meth) acrylate, nourphenol polyethylene oxide (n = 4 or more) modified (meth) acrylate having a molecular weight of 325 or more are adhesives of the present invention. It is preferable because the curability and adhesiveness of the agent can be improved.

[0027] [Chemical 2]

(In the formula, R represents a hydrogen atom or a methyl group, and R ′ represents a hydrogen atom, a C 1-9 alkyl group, or a cumyl group.)

[0028] (g) Alkoxyalkylene oxide-modified (meth) acrylate having a molecular weight of 450 or more Alkoxyalkylene oxide-modified (meth) atelate is the terminal hydroxyl group of alkoxyalkylene oxide or alkoxypolyalkylene oxide. This is a product obtained by condensation reaction with rillic acid. Preferred examples of alkoxy include methoxy and ethoxy. Examples of the alkoxyalkylene oxide include alkoxypolyethylene oxide.

Examples thereof include alkoxy (preferably methoxy) polyethylene glycol mono (meth) acrylate represented by the following formula.

[0029] [Chemical 3]

(In the formula, R represents a hydrogen atom or a methyl group, and R ′ represents a methyl group or an ethyl group.)

[0030] (h) Alkyleneoxide-modified (meth) acrylate of bisphenol A or bisphenol F having a molecular weight of 60 or more

Bisphenol A alkylene oxide modified (meth) acrylate is one or both (preferably both) hydroxyl groups of bisphenol A modified with alkylene oxide ( It is modified by (meth) acrylate.

Further, the alkylene oxide-modified (meth) acrylate of bisphenol F is one in which one or both (preferably both) hydroxyl groups of bisphenol F are modified by alkylene oxide-modified (meth) acrylate.

Examples thereof include bisphenol A polyethylene oxide-modified di (meth) tarate represented by the following formula.

[0031] [Chemical 4]

(In the formula, R independently represents a hydrogen atom or a methyl group.)

[0032] (Li) Polyalkylene glycol-modified (meth) acrylate having a molecular weight of 520 or more

Examples thereof include polyethylene glycol di (meth) acrylate and the like represented by the following formula.

[0033] [Chemical 5]

(In the formula, each R independently represents a hydrogen atom or a methyl group.)

[0034] (nu) Other (meth) acrylates having a molecular weight of 600 or more include, for example, polyurethane (meth) acrylate.

[0035] The upper limit of the molecular weight of the (meth) atalylates (i) to (nu) is not particularly set.

[0036] As described above, the component (A) composed of a polymerizable monomer, preferably 80% by mass or more is selected from (meth) acrylates described in (i) to (nu) 1 or 2 or more An optional component other than the force (ii) to (nu) which is a combination of the above may be included. As an optional component other than (i) to (nu), for example, (meth) acrylic acid is preferably mentioned. By including a strong component, the adhesive of the present invention can impart good mechanical strength and adhesiveness. [0037] The content of the (meth) acrylic acid and the low-molecular polymerizable (meth) acrylate having a carboxyl group in the component (A) is usually 20% by mass or less, preferably 10% by mass or less. . If it exceeds 20 mass%, the solubility of the adhesive of the present invention in a polystyrene-based resin foam may increase. Therefore, when the adhesive is applied to the polystyrene-based resin foam, the foam is dissolved and air contained in the foam is mixed with the adhesive. For this reason, the radical polymerization reaction of the adhesive is inhibited by the mixed air, and the curing rate may be remarkably slowed. In addition, the adhesive strength may be weakened.

[0038] The component (B) composed of the organic peroxide can act as a radical initiator in the adhesive of the present invention or as a redox polymerization initiator together with the component (C). In other words, the component can initiate the addition polymerization reaction or curing reaction of the component (A). As the component (B), a known organic peroxide can be arbitrarily used as a radical initiator. For example, t-butyl hydride peroxide, p-menthane hydride peroxide, cumene hydride peroxide, diisopropyl Hydroperoxides such as benzene hydride peroxide; Peroxyesters such as _t- butyl peroxylaurate, t-butyl peroxybenzoate, t-butyl peroxydecanoate; 1, 5 di —T Peroxyketals such as butylperoxy-3,3,5-trimethylcyclohexane; ketone peroxides such as acetoacetyl peroxide; disilver oxides such as benzoyl peroxide.

Of these, hide mouth peroxides are preferred because they can enhance the adhesiveness of the adhesive of the present invention.

[0039] The content of the component (B) in the adhesive of the present invention is usually 0.5 to 5 parts by mass, more preferably 1 to 4 parts by mass with respect to 100 parts by mass of the component (A). is there. When the content is less than 0.5 parts by mass, the curing rate of the adhesive is slowed, which is unfavorable. On the other hand, when the content exceeds 5 parts by mass, the physical properties such as adhesive strength are rather lowered.

[0040] The component (C) composed of the vanadium compound can act as a radical generation accelerator or together with the component (B) as a redox polymerization initiator.

Component (A) consisting of a polymerizable monomer and an organic peroxide that acts as a radical initiator When the adhesive containing the component (B) is cured by radical polymerization and is brought into contact with air, the radical polymerization reaction is inhibited by oxygen in the air, so that it is difficult to cure. In particular, a large amount of air is also present on the adhesive surface of the polystyrene-based resin foam that can be the adherend of the adhesive of the present invention (the adhesive surface is usually a cut surface of the foam, Since air exists), when an adhesive is applied to the foam, the radical polymerization reaction is hindered and the curability tends to deteriorate soon. Therefore, the adhesive of the present invention preferably contains a component (C) composed of a vanadium compound.

As the component (C), vanadyl acetylacetonate, vanadium acetylacetonate, vanadyl naphthenate, or the like is used.

The content of the component (C) in the adhesive of the present invention is preferably 0.02 to 3 parts by mass with respect to 100 parts by mass of the component (A). Is more preferable.

[0041] The component (D) composed of the acidic phosphate compound can act as a storage stabilizer for the polymerizable monomer (A). Further, it can act as an auxiliary agent for the redox polymerization initiator having the component (B) and component (C).

As component (D), methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, phenol phosphate, diphenyl phosphate, mono (meth) acryloyloxychetyl phosphate, di (meth) allyloyl Acid phosphoric esters such as oxetyl phosphate; Phosphonic acids such as phenylphosphonic acid and diphenylphosphonic acid; Phosphophosphonic acids such as phenylphosphonous acid and diphenylphosphonous acid; Ethyl pyrophosphate, Butylpyrophosphate Acid pyrophosphates such as phosphates; phosphorous oxyacids such as phosphoric acid, phosphorous acid, pyrophosphoric acid and polyphosphoric acid are used.

The content of the component (D) in the adhesive of the present invention is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the component (A), and is 0.2 to 3 parts by mass. Is more preferable.

[0042] Furthermore, the adhesive of the present invention can contain an a-hydroxycarbo-louie compound as an optional component. The a-hydroxycarbonyl compound can further improve the curing rate of the adhesive of the present invention.

Examples of the a-hydroxycarbol compound include carboxylic acids, carboxylic acid esters, ketones and aldehydes having a hydroxyl group at the α-carbon of the carbo group. Specifically, for example, 1) _a -hydroxycarboxylic acid such as lactic acid, tartaric acid, malic acid, glycolic acid, and quenoic acid, 2) α-hydroxycarboxylic acid ester such as methyl lactate, ethyl lactate, and ethyl glycolate, 3) _α- ketols such as hydroxyacetone, dihydroxyacetone, acetoin, benzoin and the like, and 4) addition reaction product of _a -hydroxycarboxylic acid with an epoxy compound or oxazoline compound. These may be contained alone or in combination of two or more.

The content of the ex-hydroxycarbon compound in the adhesive of the present invention is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of component (A). More preferably, it is 3 parts by mass.

[0043] Further, the adhesive of the present invention may contain a component that can further enhance the storage stability of the component (A) (including polymerizable (meth) acrylate), such as a radical polymerization inhibitor. Examples of radical polymerization inhibitors include 2,6-di-tert-butyl-4-methylfail, 2,2-methylenebis (4-methyl-6-tert-butylphenol), benzoquinone, hydroquinone, methylhydroquinone, ethylenediamine 4-acetic acid, 4 sodium salt, oxalic acid, N —Methyl N-trosorrin, N ditrosodiphenyl, etc.

[0044] Furthermore, the adhesive of the present invention may contain an organic filler. Examples of the organic filler include acrylonitrile-butadiene-styrene copolymer (ABS resin), methyl methacrylate-butadiene styrene copolymer (MBS resin), methyl methacrylate-butadiene-acrylo-tolulu styrene copolymer. Forces including thermoplastic resin such as (MBAS resin) are not limited to these. The organic filler can adjust the viscosity of the adhesive of the present invention and can impart toughness to the cured product of the adhesive.

Furthermore, the adhesive of the present invention can also contain dyes, pigments and the like.

Here, the optional components contained in the adhesive of the present invention (including radical polymerization inhibitors, dyes and pigments) are preferably basically organic substances so as not to increase the amount of adhesive combustion residue. Needless to say,

[0045] The adhesive of the present invention is stored in two parts until it is used (hereinafter, these two parts are also referred to as "X agent and Y agent"). Both agent X and agent Y preferably contain component (A), but components (B) and (C) should not coexist in separate agents. Preserved (for example, the organic peroxide (B) is contained only in the X agent and the vanadium compound (C) is contained only in the Y agent). This is to prevent the curing reaction from starting during storage.

The component (D) may be contained in either the X agent and / or the Y agent, but is preferably contained in the same agent as the (C) vanadium compound. This is because it can act as a storage stabilizer.

The composition of the polymerizable monomer of component (A) contained in agent X and the composition of the polymerizable monomer of component (A) contained in agent Y may be the same or different, but preferably Are the same.

By dividing into two agents, X agent and Y agent, it is possible to store it until it is prepared and used until it is used, and it is convenient because it can be stored again after use.

[0046] The viscosity of the X agent and the Y agent constituting the adhesive of the present invention is preferably 50 to 20000 mPa.s, more preferably 300 to 5000 mPa's. The viscosity can be adjusted as appropriate by selecting the composition of the polymerizable monomer (A) and blending the organic filler.

When the viscosity of the X agent or Y agent is less than 50 mPa's, it tends to penetrate into the adherend when it is applied to the adherend, and the adhesive strength tends to be insufficient. On the other hand, when the viscosity of the X agent or Y agent exceeds 20000 mPa's, it becomes difficult to uniformly apply to the coating surface of the adherend, and strong pressing after bonding tends to be required, and the curing rate tends to be slow. There is.

[0047] It is preferable that the X agent and the Y agent constituting the adhesive of the present invention have low solubility in the polystyrene-based resin foam. The low solubility means that X agent or Y agent is applied at a temperature of 23 ° C; 50% RH in a constant temperature and humidity chamber, and 0. lgZcm ^{2 is} applied to the smooth surface of the polystyrene resin foam. This means that the depth force of the depression formed in the polystyrene-based resin foam when wiped off after 10 minutes is 0.2 mm or less.

Here, for example, Kanepal R (Kane force Co., Ltd .; trade name) can be used as the polystyrene-based resin foam. “Smooth surface” means a surface roughness profile measuring machine (Surfcom 570A (manufactured by Tokyo Seimitsu Co., Ltd.)) under the conditions of measurement speed = 0.3 mm / sec and measurement length = 10 mm. A surface whose maximum height difference when measured is 50 m or less. “Wipe off” means to use a clean cloth that can absorb the agent and gently wipe it with a hand to avoid damaging the foam.

[0048] The curing time of the adhesive of the present invention is preferably in the range of 10 seconds to 5 minutes. When cured The interval can be adjusted by appropriately changing the types and contents of the organic peroxide (B), the vanadium compound (C), and the acidic phosphate compound (D).

The curing time is about −10 ° C. to 35 ° C. The adhesive of the present invention is mixed with 0.5 g each of the X agent and the Y agent in a 2.5 ml polyethylene container. It can be measured by measuring the time to cure.

[0049] The mass of the combustion residue of the cured product of the adhesive of the present invention is preferably 4% or less with respect to the mass of the cured product before combustion. The mass of the combustion residue is set by curing the adhesive of the present invention obtained by mixing the X agent and the Y agent (preferably by equal mass mixing) at 23 ° C, 50% RH constant temperature and humidity. And measure the mass after combustion by heating the resulting cured product (preferably about 1 mg) to a temperature of 10 ° CZmin at 20 ° C and 800 ° C in an argon atmosphere. Can be obtained.

[0050] An example of measuring the mass of the combustion residue will be specifically described.

A cured product obtained by mixing an equal mass of the X agent and Y agent of the adhesive of the present invention in a constant temperature and humidity room at 23 ° C and 50% RH, under the following conditions in accordance with JIS K7120 Perform differential thermal analysis and measure the weight of the combustion residue. The obtained results are shown as a residual rate (%).

Sample: Measured in lOmg in a 5φ platinum open sample container

Measurement temperature: 20 ~ 800 ° C, temperature rising speed = 10 ° CZmin, measurement completed when 800 ° C is reached

Argon air flow: 300ml / min

[0051] The amount of combustion residue can be determined by, for example, 1) reducing the amount of vanadium compounds and other additives that are likely to remain as combustion residues, and 2) selecting a monomer containing a large amount of oxygen atoms as component (A). Can be adjusted (reduced).

[0052] The Shore hardness D of the cured product of the adhesive of the present invention is preferably set to 60 or less, more preferably 50 or less. Here, the Shore hardness D is determined by curing the adhesive of the present invention obtained by mixing the X agent and the Y agent (preferably by equal mass) in a constant temperature and humidity of 23 ° C and 50% RH. It means the Shore hardness of the obtained cured product.

The hardness is adjusted by selecting the composition of the polymerizable monomer (A) and the type and amount of organic filler. It can be done by changing as appropriate.

If the Shore hardness D exceeds 60, the cured product of the adhesive that protrudes from the adhesive surface after bonding may be too hard and damage the adherend when removed.

[0053] The adhesive of the present invention can be produced by the same method as the ordinary two-component acrylic adhesive, except that the essential components (A) to (D) are blended. For example, it can be produced by the procedure shown below.

Ingredients (A) and (D) are charged into a stainless steel container, and while stirring, add additives such as stabilizers and viscosity modifiers as necessary, and stir until uniform. If it is difficult to dissolve or evenly disperse the additive, the system can heat the system to a temperature of 80 ° C or lower, with the ability to hold the dissolved or dispersed additive in a readily soluble component. To do. After that (when heated, cool to 35 ° C or lower), add component (B) and stir to obtain agent X.

Similarly, components (A) and (D) are charged into a stainless steel container, and while stirring, components (C) and additives such as stabilizers and viscosity modifiers are added as necessary, and stirred until uniform. Y agent is obtained. If it is difficult to dissolve or evenly disperse the additive, heat the system to a temperature of 80 ° C or less, the force to add the dissolved or dispersed additive to the easily soluble component.

[0054] The adhesive of the present invention can adhere an arbitrary adherend, but is preferably used for bonding a polystyrene-based resin foam described later. Although any method can be adopted as the bonding method, it is preferable to employ 1) a honeymoon bonding method or 2) a single-side bonding method.

[0055] 1) In the honeymoon bonding method, when adhering materials 1 and 2 are bonded together, one of the two agents (X agent) of the adhesive of the present invention is applied to adhering material 1, and the adhering material 2. Apply the other of the two types of acrylic adhesive for building a vertical model (Y agent). Next, the adhesive-coated surfaces of the adherend 1 and the adherend 2 to which the X agent and the Y agent are applied are bonded together.

As a method for applying the X agent or the Y agent, a known application method such as a brush coating method, a roll coater method, or a spray method can be used.

Further, if necessary, the bonded adherends 1 and 2 are pressed and Z or temporarily fixed. Specifically, it can be clamped, applied with weight, It is possible to use a method such as pressurizing with a gas.

[0056] 2) In the single-sided bonding method, when bonding the adherends 1 and 2, both the two adhesives (X agent and Y agent) of the present invention are applied to the adherend 1. Here, X agent and Y agent may be applied separately, or a mixture obtained by mixing X agent and Y agent in advance may be applied. When X agent and Y agent are applied separately, it is preferable to apply using a mixing brush and apply, and then mix X agent and Y agent on the application surface. In addition, when the X agent and the Y agent are mixed and applied in advance, they can be mixed using a known mixer and can be applied using a mixing brush. It is preferable that the adhesive applied to the adherend 1 is thinly applied to the entire application surface of the adherend 1. In order to apply the adhesive thinly over the entire application surface, the applied adhesive can be stretched using a brush or a bar coater. Alternatively, the X agent and the Y agent can be pressurized and supplied to a static mixer, mixed, and sprayed on the mixture 1 to be applied to the adherend 1. In this way, the process of mixing the X agent and the Y agent, the process of applying the mixture to the adherend 1 and the process of extending it thinly can be completed at the same time, which is the most efficient.

The adherend 1 to which the adhesive is applied is bonded to the adherend 2.

Further, the bonded adherends 1 and 2 can be pressed and Z or temporarily fixed. Specifically, it is possible to adopt a method such as clamping with a clamp, applying a load, or pressurizing with a cold press.

[0057] <Adhesive Adhesive Material of the Present Invention>

As described above, the adhesive of the present invention can be bonded to any one, but is particularly suitable for bonding polystyrene-based resin foams. That is, a preferable adherend of the adhesive of the present invention is a polystyrene-based resin foam (however, it is not limited thereto). Hereinafter, a preferred polystyrene-based resin foam as an adherend will be described.

[0058] The polystyrene-based resin foam that can be the adhesive material of the present invention foams a polystyrene-based resin containing a foaming agent (hereinafter also referred to as "expandable polystyrene-based resin"). It can be manufactured from Kotoko. The foaming polystyrene-based resin can be foamed by in-mold foaming using a heat medium such as water vapor, or by extrusion foaming. Arbitrary methods, such as a method of making them, can be adopted.

The expansion ratio of the polystyrene-based resin foam is preferably about 1.6 to 200 times, more preferably about 15 to 80 times, but is not limited thereto.

[0059] The expandable polystyrene resin can be produced by adding a foaming agent to the polystyrene resin (for example, impregnating the foaming agent).

As the blowing agent, C3 to C5 hydrocarbons such as propane, isobutane, normal butane, isopentane, normal pentane, neopentane, and other aliphatic hydrocarbons are most preferable. Further, carbon dioxide gas or the like can be used. Also, volatile blowing agents such as difluoroethane and tetrafluoroethane, which have zero or less ozone depletion potential, such as fluorofluorocarbons, can be used. These foaming agents can be used in combination.

[0060] Examples of the method of adding a foaming agent to the polystyrene-based resin include a method of suspending a polystyrene-based resin in an aqueous medium and press-impregnating the foaming agent. Alternatively, polystyrene-based resin and foaming agent may be melt-mixed using an extruder. Alternatively, when the polystyrene-based resin is produced by suspension polymerization, the foaming agent can be included in the polystyrene-based resin by adding a foaming agent during the polymerization process or after the completion of the polymerization process.

[0061] The expandable polystyrene-based resin is preferably in the form of particles. The particulate foamable polystyrene resin can be obtained, for example, by impregnating a foaming agent during or after the polymerization when producing a polystyrene resin by suspension polymerization. However, polystyrene foam obtained by other polymerization methods (for example, bulk polymerization method) is pelletized to form particles, and this is impregnated with a foaming agent to form particulate foamable polystyrene. You can also obtain rosin.

The particle size of the particulate foamable polystyrene-based resin is preferably about 0.2 to 4 mm, more preferably about 0.5 to 2 mm.

The particulate foamable polystyrene-based resin can be foamed with or without pre-foaming. However, when the foamed polystyrene-based resin is pre-foamed by heating with steam or the like, it is good polystyrene foam. A foam can be obtained. [0062] As described above, the expandable polystyrene-based resin is a polystyrene-based resin containing a foaming agent. As the polystyrene-based resin, any polystyrene-based resin can be used without particular limitation. it can. The molecular weight of the polystyrene-based resin is an arbitrary force, preferably 100,000 to 500,000, more preferably about 250,000 to 350,000, but is not limited thereto.

[0063] The polystyrene-based resin is obtained by polymerizing a styrene-based monomer. Examples of the styrene monomer include styrene and styrene derivatives such as α-methylstyrene, paramethylstyrene, t-butylstyrene, and chlorostyrene. The styrene monomer to be polymerized may be one kind or a mixture of two or more kinds.

Further, a styrene monomer and a subordinate monomer other than the styrene monomer copolymerizable with the styrene monomer may be copolymerized.

Examples of monomers other than the styrenic monomer include (meth) acrylic acid esters such as methyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, cetyl methacrylate, and (meth) Acrylic acid and monofunctional monomers such as acrylonitrile, dimethyl fumarate, ethyl fumarate, maleic acid, maleic anhydride, etc., and polyfunctional monomers such as difunctional benzene, alkylene glycol dimethacrylate, etc. The body is mentioned. One or more of these monomers can be copolymerized with a styrenic monomer.

[0064] The method for polymerizing the styrenic monomer (and other monomers if necessary) is not particularly limited, and suspension polymerization method, bulk polymerization method, emulsion polymerization method and the like can be employed. . As described above, when a styrene monomer is dispersed in water with a dispersant and the like, and a polymerization initiator is added and polymerized by suspension polymerization or the like, the foaming agent is impregnated during or after the polymerization. Thus, a particulate foamable polystyrene resin can be obtained.

[0065] <Method for producing vanishing model for fabrication of the present invention>

The present invention relates to a method for producing a disappearance model for fabrication made of polystyrene-based resin foam (hereinafter also referred to as “method of the present invention”). The method of the present invention is characterized by using the above-mentioned adhesive of the present invention, but otherwise normal means can be applied as appropriate. Here, “disappearance model for fabrication made of polystyrene-based resin foam” A disappearance model for fabrication based on a fat foam is intended. Of polystyrene foams, polystyrene foam is most preferably exemplified as the base material of the disappearance model for fabrication. This is because of cost and performance.

That is, the method of the present invention includes: 1) preparing a plurality of model parts (including model part 1 and model part 2) that constitute a disappearance model for fabrication made of polystyrene-based resin foam; and 2) It includes a step of bonding the plurality of model parts at their joint surfaces, and the bonding in the step 2) is performed using the adhesive of the present invention.

However, in the method of the present invention, the step 1) or 2) may be changed as appropriate, and any method other than these steps may be included in the scope of the present invention.

[0067] The method of the present invention is characterized in that the bonding in the step 2) is performed by using the adhesive of the present invention. The bonding is performed by a honeymoon bonding method or a single-side coating bonding method. More preferably, the honeymoon bonding method is used. Hereinafter, each bonding method will be described.

[0068] The honeymoon bonding method is: a) a step of applying the X agent of the adhesive of the present invention to the joint surface of one of a plurality of model parts (hereinafter referred to as model part 1); b) a plurality of models Applying a Y agent of the adhesive of the present invention to the joint surface of another one of the parts (hereinafter referred to as model part 2), and c) joining the joint surface of model part 1 and model part 2 It includes a step of bonding the surface.

The application in the step a) or b) can be performed using a known application method such as a brush coating method, a roll coater method, or a spray method.

[0069] In addition, the honeymoon bonding method may further include a step of d) pressing and Z or temporarily fixing the bonded model parts 1 and 2 as necessary. Clamping and Z or temporary fixing can be performed using a method such as clamping with a clamp, applying a load, or pressing with a cold press.

That is, as the step (a), when adhering the adherends 1 and 2 made of foamed polystyrene-based resin, the X agent of the acrylic adhesive for manufacturing the vertical model is applied to the adherend 1. Also Then, apply Y agent of acrylic adhesive for vertical model manufacturing to adherend 2. In this case, specifically, a known coating method such as a brush coating method, a roll coater method, or a spray method can be used. Next, as the step (b), the adhesive application surfaces of the adherends 1 and 2 to which the X agent and the Y agent are respectively applied in the step (a) are bonded together. Further, as necessary, as a step (c), the bonded substrates 1 and 2 are pressed and Z or temporarily fixed. Specifically, it is possible to use a method such as clamping with a clamp, applying a load, or applying pressure with a cold press.

[0070] The single-sided application bonding method is a) a step of applying the X and Y agents of the adhesive of the present invention to the bonding surface of one of a plurality of model parts (model part 1), and b ) It includes a step of bonding the joint surface of the model part 1 and the joint surface of another model part (model part 2).

[0071] The application of the X agent and the Y agent in the step a) may be performed by previously applying a mixture obtained by mixing the X agent and the Y agent to the joint surface of the model part 1. And Y agent can be applied separately to the joint surface of the model part 1 and mixed together.

When X agent and Y agent are applied separately and mixed together, it is preferable to apply and mix using a mixing brush. In addition, when the X agent and the Y agent are mixed in advance, they can be mixed using a known mixer, a mixing iron, or a brush.

[0072] It is preferable that the X agent and the Y agent applied in the step a) are thinly stretched over the entire joint surface. In order to extend the X agent and Y agent thinly on the entire joint surface, a brush or a bar coater can be used.

[0073] As a preferred mode of application in the step a), the X agent and the additive are pressurized and supplied to a static mixer and mixed, and this mixed solution is sprayed on the front surface of the joint surface of the model part 1. And apply. In this way, the mixing of the X agent and the Y agent, the application of the obtained mixed solution, and the thin application of the applied adhesive are performed in one step, which is efficient.

[0074] Further, the mixed bonding method includes a step of c) pressing and Z or temporarily fixing the bonded model parts 1 and 2 as necessary. Clamping and Z or temporary fixing can be performed using methods such as clamping, applying weight, or pressing with a cold press. It can be carried out.

[0075] According to the method of the present invention, the disappearance model for forging can be produced in a short time and easily. Further, in the vanishing model for fabrication manufactured by the method of the present invention, each model part is strongly bonded, and the dimensional error is small and the combustion residue is further reduced. Therefore, the product manufactured by the disappearance model forging method using this disappearance model for forging has high dimensional accuracy, and it is said that deterioration in strength due to adhesion and intrusion of combustion residues and poor workability are suppressed. Have the advantage.

Example

[0076] The ability to explain the present invention in more detail with reference to the following examples. These examples are given by way of illustration, and the scope of the present invention should not be construed as being limited by these examples! /, That's it!

[0077] The adhesives in the following examples and comparative examples are the X agent and the Y agent, the X agent contains the (B) component (organic peroxide), and the Y agent contains the (C) component ( Vanadium compounds).

[0078] Each adhesive in the examples and comparative examples was evaluated for the following items (1) to (4).

(1) Solubility of each of the X agent and Y agent composing each adhesive in polystyrene-based resin foam

(2) Set time when polystyrene resin foam is bonded using each adhesive

(3) Adhesive strength when polystyrene resin foam is bonded using each adhesive

(4) Combustion residue value of cured product of each adhesive

[0079] In the following, specific evaluation methods will be described for the above (1) to (4). Here, Kanepal R (manufactured by Kane force Co., Ltd.) was used as the polystyrene-based resin foam.

(1) Solubility of X agent and Y agent in the adherend

Smoothing of polystyrene resin foam foam (surface roughness profile measuring machine (Surfcom 570A (manufactured by Tokyo Seimitsu Co., Ltd.)), X agent or Y agent 0.lg in a constant temperature and humidity room of 23 ° C, 50% RH ) Was applied to a square area of surface lcm ² where the maximum surface height difference was 50 m or less when measured under the conditions of measurement speed = 0.3 mm / sec and measurement length = 10 mm. After 10 minutes, apply the applied X or Y agent to the foam using a clean cloth that can absorb the agent. It was wiped lightly by hand so that the applied surface was observed. The depth at which the surface was melted and recessed was measured.

[0080] (2) Set time

In a constant temperature and humidity room at 23 ° C. and 50% RH, an adhering material 1 and an adhering material 2 made of polystyrene resin foam having dimensions of 20 × 40 × 50 mm were prepared. The X agent (0. lg) was applied to the 20 X 40 mm surface of the adherent 1 and the Y agent (0. lg) was applied to the 20 X 40 mm surface of the adherent 2 using a hand roller. After 1 minute of open time, the coated surfaces were bonded together (honeymoon bonding). Pressure: Clamped at 49 NZm ^{2 for} 3 minutes to produce an adhesive with a length of 100 mm, a width of 40 mm, and a thickness of 20 mm.

The bending strength was measured every predetermined time (every minute) from the start of pressing, and the time when a strength of 9.8 NZcm ² or more was obtained was taken as the set time.

The bending strength was measured according to JIS K7171 at a fulcrum distance of 70 mm and a test speed of 20 mmZ.

[0081] (3) Adhesive strength

An adhering material 1 and an adhering material 2 made of polystyrene resin foam having dimensions of 20 × 40 × 100 mm were prepared in a constant temperature and humidity chamber at 23 ° C. and 50% RH. The X agent (0. lg) was applied to the 20 X 40 mm surface of Adhesive 1 and the Y agent (0. lg) was applied to the 20 X 40 mm surface of Adhesive 1 using a hand roller. After 1 minute of the open time, the coated surfaces were bonded together (no nemon bonding). Pressure: Clamped at 49 NZcm ^{2 for} 3 minutes to produce an adhesive body having a length of 100 mm, a width of 40 mm, and a thickness of 20 mm.

The bending strength was measured 24 hours after the start of pressing. The bending strength was measured according to JIS K7171 at a fulcrum distance of 70 mm and a test speed of 20 mmZ.

[0082] (4) Measurement of combustion residue value

In a constant temperature and humidity room at 23 ° C and 50% RH, the X agent and Y agent constituting each adhesive were mixed in equal mass and cured. The lOmg of the obtained cured product was subjected to differential thermal analysis under the following conditions in accordance with JIS K7120, and the mass of the combustion residue was measured. The obtained results are shown by the survival rate (%).

Residual rate (%) = measured mass of combustion residue (mg) ZlOmg X 100 [0083] Measuring equipment: TGZDTA220 manufactured by Seiko Electronics Industry Co., Ltd.

Sample: Measured in lOmg in a 5φ platinum open sample container

Anolegon Airflow: 300ml / min

[0084] [Examples 1 to 4, Comparative Example 1]

Adhesives such as X agent and Y agent shown in Table 1 were prepared. Each adhesive was evaluated for performance as described above. The results are shown in Table 1.

[0085] [Table 1]

In Table 1 above,

1) M-5300 is a product of ω-carboxypolypropylatetone (η = 2) acrylate manufactured by Toagosei Co., Ltd.

2) Μ-102 means phenoxyethylene oxide modified (η = 4) from Toagosei Co., Ltd. Related,

3) M-90G is methoxypolyethylene glycol (n = 9) metatalylate manufactured by Shin-Nakamura Chemical Co., Ltd.

4) BPE-500 is an ethylene oxide modified (n = 10) dimetatalylate of bisphenol A manufactured by Shin-Nakamura Chemical Co., Ltd.

5) 14G means polyethylene glycol (n = 14) dimethacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.

[0087] The adhesives of Examples 1 to 3 were configured such that (A) the polymerizable monomer was composed only of a polymerizable (meth) acrylate which was selected from polymerizable (i) to (ri). It is a two-component acrylic adhesive. Further, the adhesive of Example 4 has a polymerizable property in which 90% by mass of (A) the polymerizable monomer is selected from (i) to (i).

This is a two-component acrylic adhesive that is (meth) acrylate and the remaining 10% by mass is methacrylic acid (molecular weight: 86) not belonging to (i) to (ri).

On the other hand, in the adhesive of Comparative Example 1, (A) 70% by mass of the polymerizable monomer is a polymerizable (meth) acrylate which is selected from (i) to (i), and the remaining 30% by mass is A two-component acrylic adhesive that is methacrylic acid (molecular weight: 86).

[0088] The adhesives of Examples 1 to 4 have 1) no solubility in the adherend, 2) a short set time, and 3) high adhesive strength compared to the adhesive of Comparative Example 1. I understand that. Also, like Comparative Example 1, it is obvious that there are few combustion residues.

Of the adhesives of Examples 1 to 4, the adhesives of Examples 3 and 4 gave good results in terms of set time. This is presumably because the ratio of polymerizable (meth) acrylate having a large molecular weight is higher than that of the adhesive of Example 2.

[0089] [Examples 3 to 4, Comparative Examples 2 to 3]

An adhesive consisting of the X agent and the Y agent shown in Table 2 was prepared. Various prepared adhesives

The performance was evaluated together with a commercially available two-component epoxy adhesive (Comparative Example 4). The epoxy adhesive of Comparative Example 4 was tested by mixing the main agent and the curing agent at 1: 1 (mass ratio). These results are shown in Table 2.

[0090] [Table 2]

In Table 2 above,

6) HO MS is succinic acid 2-methacryloyloxetyl manufactured by Kyoeisha Chemical Co., Ltd.

7) M—600A is 2-hydroxy-3phenoxypropyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd.

8) BPE-1300 is a bisphenol A ethylene oxide manufactured by Shin-Nakamura Chemical Co., Ltd. (n = 30) Modified metatarylate

9) Two-part epoxy adhesive is made by Vantico A & T US Inc. Fast-curing two-part epoxy adhesive EPibond 1217—A / B

[0092] The adhesive of Example 5 is the two-part acrylic adhesive of the present invention using vanadyl acetylyl acetate as a reducing agent.

The adhesive of Comparative Example 2 or 3 is the same as that of Example 5 except that ethyl lentiourea or benzoylthiourea, which is a general radical generation accelerator, is used as the reducing agent.

The adhesive of Comparative Example 4 is a commercially available two-part epoxy adhesive.

[0093] The adhesive of Example 5 has a significantly shorter set time than the adhesives of Comparative Examples 2 to 4.

It can be seen that the adhesive strength is high. It can also be seen that the combustion residue is extremely small compared to the adhesive of Comparative Example 4.

[0094] [Example 6]

Using the adhesive of Example 5, the set time and adhesive strength in the single-sided coating adhesive method were measured. X and Y agents were each applied to adherend 1 in an amount of 0.1 lg, mixed with a mixing trowel, spread over the entire adhesive surface, and immediately attached to adherend 2. The methods for measuring the dimensions of the adherend, pressing, and adhesive strength were the same as in Examples 1-5. The set time was the time at which a strength of 9.8 NZcm ² or more was obtained by measuring the bending strength for each mixing start force (every minute).

Set time 9 minutes and the tongue bonding strength was good and 34. 3NZcm ^2.

Industrial applicability

[0095] According to the present invention, there is provided an acrylic adhesive for producing vertical models having improved curability with low solubility in expanded polystyrene-based resin. By using this adhesive, it is possible to reduce the smoke and combustion residue generated when burning the disappearance model for fabrication, and it is possible to make a highly accurate mold form.

Moreover, if the construction method provided by the present invention is used, the saddle model can be manufactured in a short time.

Claims

The scope of the claims

(A) a polymerizable monomer, (B) an organic peroxide, (C) a vanadium compound, and (D) an acidic phosphate compound, and (B) and (C) do not coexist. An acrylic adhesive that can be stored separately.

(I) Alkyl (meth) acrylate with a molecular weight of 295 or more

(Mouth) Alicyclic (meth) acrylate with molecular weight of 195 or more

(E) Polyester with a molecular weight of 230 or more (Meth) acrylate

(Nu) Other (meth) acrylate with a molecular weight of 600 or more

2. The acrylic adhesive according to claim 1, wherein one of the two agents is placed on a smooth surface of a polystyrene-based resin foam in a constant temperature and humidity chamber at 23 ° C. and 50% RH in an amount of 0.1 lgZcm. ^2. Adhesive characterized in that the depth of the recess formed in the polystyrene-based resin foam when the applied agent is wiped off after 10 minutes is 0.2 mm or less.

2. The acrylic adhesive according to claim 1, wherein the mass of a cured residue (combustion condition: 800 ° C. under argon atmosphere) cured at 23 ° C. in a constant temperature and humidity chamber of 50% RH An adhesive characterized by being 4% or less of the mass of the cured product before burning.

A disappearance model for fabrication made of polystyrene resin foam, including the step of bonding the respective joint surfaces of the model part 1 and model part 2 constituting the disappearance model for fabrication made of polystyrene resin foam. A method of manufacturing, wherein the laminating step includes: (a) applying one of the two acrylic adhesives according to claim 1 to the joint surface of the model part 1,

(b) applying the other of the two acrylic adhesives according to claim 1 to the joint surface of the model component 2, and

A disappearance model for fabrication made of polystyrene resin foam, including the step of bonding the respective joint surfaces of the model part 1 and model part 2 constituting the disappearance model for fabrication made of polystyrene resin foam. A method of manufacturing, wherein the laminating step includes:

(a) applying both of the two adhesives according to claim 1 to the joint surface of the model part 1, and

(b) A method including a step of bonding the joint surface of the model part 1 and the joint surface of the model part 2 together.