KR20190027156A - Adhesive composition for artificial marble - Google Patents

Abstract

The present invention relates to an adhesive composition for artificial marble used for cutting and bonding an acrylic artificial marble plate material and, more specifically, to an adhesive composition for artificial marble, which improves discoloration resistance of light, that is, light resistance, has good initial color of an adhesive, and satisfies required adhesive strength by including a thiol-based polymerization retarder in a specific amount.

Description

[0001] Adhesive composition for artificial marble [0002]

The present invention relates to an adhesive composition for an artificial marble used for cutting and bonding an acrylic artificial marble plate material, and more particularly, to an adhesive composition for artificial marble which comprises a thiol-based polymerization retarder in a specific amount, To an adhesive composition for artificial marble, which improves light fastness and satisfies the required adhesive strength with good initial color of the adhesive.

Artificial marble is used as a high-grade interior building material, for example, for various purposes such as table plates, bathtubs, sinks, kitchen countertops, ornaments and materials for common display shelves.

Such an artificial marble uses an acrylic adhesive such as an acrylic adhesive disclosed in Korean Patent Registration No. 10-0468645 for cutting and sticking a plate material during processing. In general, acrylic adhesive has low light resistance and yellowing occurs over time There was a problem.

Therefore, there has been an attempt to improve the light resistance by adding an ultraviolet stabilizer. However, when the content of the ultraviolet stabilizer is increased, the yellow color of the initial color of the adhesive increases, and the joint of the adhesive portion is not smooth.

KR 10-0468645 B (Notification Date: January 31, 2005)

The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide an adhesive composition for artificial marble, which is improved in light resistance and satisfactory in initial color of adhesive, and satisfies required adhesive strength.

In order to achieve the above object,

A subject comprising 0.01-0.8 parts by weight of a thiol-based polymerization retarder based on 100 parts by weight of an acrylic resin syrup; And curing agents; To provide an adhesive composition for artificial marble.

The adhesive composition for artificial marble of the present invention contains a specific amount of a thiol-based polymerization retarder and has an excellent light fastness, good initial color of the adhesive, and satisfactory adhesion strength required.

The present invention relates to a toner comprising 0.01 to 0.8 parts by weight of a thiol-based polymerization retarder based on 100 parts by weight of an acrylic resin syrup; And curing agents; To an adhesive composition for artificial marble.

The acrylic resin syrup may be a mixture of polymethyl methacrylate (A) and acrylic monomer (B).

The polymethyl methacrylate (A) may be a homopolymer of methyl methacrylate (a1) or a copolymer of a mixture of methyl methacrylate and another acrylic monomer (a2).

The acrylic monomer (a2) may be an alkyl acrylate monomer or an alkyl methacrylate monomer, or a mixture of an alkyl acrylate monomer and an alkyl methacrylate monomer.

Examples of the alkyl acrylate monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, Butyl acrylate, butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate, At least one selected from the group consisting of benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, glycidyl acrylate and allyl acrylate can be used.

Examples of the alkyl methacrylate monomer include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec- Acrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, butyl methacrylate, butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, Methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, glycidyl methacrylate At least one selected from the group consisting of acrylate and allyl methacrylate can be used.

Preferably, the polymethyl methacrylate is a copolymer of a mixture of methyl methacrylate and methyl acrylate.

The weight average molecular weight of the polymethylmethacrylate may be 100,000-200,000, preferably 100,000-150,000. By having the weight average molecular weight within the above range, the acrylic resin syrup can have excellent physical properties by keeping the viscosity of the acrylic resin syrup within a certain range, so that it is preferable to have the weight average molecular weight within the above range.

The polymethyl methacrylate may be contained in the acrylic resin syrup in an amount of 15-50 wt%, more preferably 20-45 wt%. If the amount is less than the above range, it is difficult to adjust the amount of the adhesive to be constant due to a decrease in the viscosity of the adhesive, and if it exceeds the above range, the viscosity of the adhesive increases to make the adhesive work difficult.

The acrylic monomer (B) is at least one monomer selected from the group consisting of methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate Acrylate, methacrylonitrile, and alpha methyl styrene in the group consisting of isopropyl methacrylate, isobutyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, styrene, It may be at least one selected.

Preferably, the acrylic monomer (B) is methyl methacrylate which is easy to handle and easy to polymerize.

The acrylic monomer (B) may be contained in the acrylic resin syrup in an amount of 50-85% by weight, more preferably 55-80% by weight. When the amount is less than the above range, the viscosity of the adhesive increases to make it difficult to discharge. When the amount exceeds the above range, the adhesive strength is lowered.

The thiol-based polymerization retarder may be any organic compound including a thiol group (-SH) for imparting light resistance to an adhesive. Any organic compound may be used without limitation, and the monofunctional thiol-based polymerization retarder and multifunctional And a thiol-based polymerization retarder may be used.

The monofunctional thiol polymerization retarder may be at least one selected from the group consisting of n-ethyl mercaptan, n-butyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, , t-dodecyl mercaptan, t-butyl mercaptan, phenyl mercaptan, benzyl mercaptan, thioglycolic acid, 3-mercaptopropionic acid, thiosalicylic acid, 2-mercaptoethanol and 3-mercapto- Propane diol, and the like.

The polyfunctional thiol-based polymerization retarder may be at least one selected from the group consisting of 1,5-pentanediol, 1,6-hexanediol, ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate) (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol bis (2-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate) Pentaerythritol tetrakis (2- Mercaptopropionate), dipentaerythritol hexacis (2-mercaptopropionate), ethylene glycol bis (3-mercaptoisobutyrate), propylene glycol bis (3-mercaptoisobutyrate) (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), propylene glycol bis (3-mercaptosuccinic anhydride) (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), butanediol bis (2-mercaptoisobutyrate), octanediol bis (2-mercaptoisobutyrate) Methylol propane tris (2-mercapto (2-mercaptoisobutyrate), ethylene glycol bis (4-mercaptovalerate), propylene glycol bis (2-mercaptobutyrate), pentaerythritol tetrakis (4-mercaptoisovalerate), diethylene glycol bis (4-mercaptovalerate), butanediol bis (4-mercaptovalerate), octanediol bis (4-mercaptovalerate) But are not limited to, propane tris (4-mercaptovalerate), pentaerythritol tetrakis (4-mercaptovalerate), dipentaerythritol hexakis (4-mercaptovalerate), ethylene glycol bis (3-mercaptovalerate ), Propylene glycol bis (3-mercaptovalerate), diethylene glycol bis (3-mercaptovalerate), butanediol bis (3-mercaptovalerate), octanediol bis (3-mercaptovalerate) Trimethylolpropane tris (3-mercaptobale < / RTI > (3-mercaptobetyrate), bisphenol A dihydroxyethyl (3-mercaptobetyrate), bisphenol A dihydroxyethyl (3-mercaptobetyrate), pentaerythritol tetrakis (3-mercaptoethyl) bis (3-mercaptopropionate), ethylene glycol bis (3-mercapto-3-phenylpropyl) (3-mercapto-3-phenylpropionate), diethylene glycol bis (3-mercapto-3-phenylpropionate), butanediol bis Propionate), octanediol bis (3-mercapto-3-phenylpropionate), trimethylolpropane tris (3-mercapto-3-phenylpropionate) 3-phenylpropionate) ethyl isocyanurate, pentaerythritol tetrakis (3-mercapto-3-phenylpropionate) and dipentaerythritol Hexa kissing can be used at least one member selected from the group consisting of (3-mercapto-3-phenyl propionate).

The thiol-based polymerization retarder is preferably a thiol-based polymerization retarder containing 4 to 12 carbon atoms, and if it is outside the above range, the smell is too strong to be used in adhesives. Therefore, .

The number of thiol groups in the thiol-based polymerization retarder is preferably 20 or less, and more preferably 16 or less. If it exceeds the above range, compatibility with other components is reduced, and the fluidity of the adhesive deteriorates, so that it is preferable to have a thiol group within the above range.

The weight average molecular weight of the thiol-based polymerization retarder may be 50-350, preferably 80-300. If the amount is less than the above range, volatilization may occur in the adhesive drying step. If the amount is outside this range, miscibility with other components may deteriorate and fluidity of the adhesive may deteriorate.

The thiol-based polymerization retarder may be added in an amount of 0.01-0.8 parts by weight, preferably 0.05-0.5 parts by weight, based on 100 parts by weight of the acrylic resin syrup. When the amount is less than the above range, the light resistance of the adhesive is lowered. If the above range is exceeded, the light resistance is excellent but the adhesive strength is lowered.

Alternatively, the subject may further include an inorganic filler to selectively increase the viscosity of the adhesive to increase initial adhesion and to reinforce the cured adhesive layer.

The inorganic filler may be at least one selected from the group consisting of aluminum trihydroxide, mica, talc, clay, calcium carbonate, and silica having a size of 0.5-5 mu m, preferably 1-2 mu m .

When the size of the inorganic filler particles is less than the above range, the amount of methyl methacrylate oil absorption increases and the raw material value increases. When the inorganic filler particle size is less than the above range, the bonding strength is lowered. Therefore, desirable.

The inorganic filler may be contained in an amount of 1-25 parts by weight, preferably 5-20 parts by weight, based on 100 parts by weight of the acrylic resin syrup. When it is less than the above range, the bonding strength is lowered, and when it exceeds the above range, the workability is lowered.

In addition, the subject matter may further comprise a crosslinking agent to chemically bond the components in the adhesive composition to form a three-dimensional network structure.

The crosslinking agent may be, for example, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, diallyl phthalate, divinylbenzene and triallylcyanur And trimethylolpropane trimethacrylate, which is capable of controlling the reaction rate and is excellent in adhesion, can be used.

The crosslinking agent may be a multifunctional monomer having a weight average molecular weight of 120 or more, preferably 250 or more, more preferably 300 or more. When the weight average molecular weight of the crosslinking agent is less than the above range, the reaction rate is too fast to be suitable for the operation, and therefore, it is preferable that the crosslinking agent has a molecular weight within the above range.

In addition, when a monofunctional monomer is used as the crosslinking agent, the reaction rate is too fast to be suitable for a work, and therefore, it is preferable to use a polyfunctional monomer.

The crosslinking agent may be included in an amount of 0.1-5 parts by weight, preferably 0.5-3 parts by weight, based on 100 parts by weight of the acrylic resin syrup. When the amount is less than the above range, the bonding strength is lowered due to the decrease in the degree of crosslinking, and when it exceeds the above range, the light resistance and storage stability are lowered.

In addition, the subject may optionally further comprise a plasticizer to impart flexibility to the acrylic resin syrup.

The plasticizer may be an amine plasticizer. Examples of the amine plasticizer include N, N-dimethyl aniline, N, N-diethylaniline, N, N-bis (2-hydroxyethyl) N, N-diethyl-p-toluidine, N-methyl-N-hydroxyethyl-p-toluidine, N, N-dimethyl-p-toluidine, (2-hydroxyethyl) -p-toluidine, alkoxylated N, N-bis- (hydroxyethyl) -p-toluidine, N, N-ethoxylated p-toluidine, and N, N-bis (2-hydroxyethyl) -xylidine.

The plasticizer may be included in an amount of 0.05-5 parts by weight, preferably 0.1-3 parts by weight, based on 100 parts by weight of the acrylic resin syrup. When the amount is less than the above range, the workability of the adhesive is deteriorated. When it exceeds the above range, the adhesive strength is lowered.

In addition, the subject may further include one or more other additives selected from ultraviolet stabilizers, curing accelerators, and coupling agents.

The ultraviolet stabilizer may be a known ultraviolet stabilizer such as N- (4-ethoxycarbonylphenyl) -N'-methyl-N'-phenylformamidine, 2- (2'- 5'-methylphenyl) benzotriazole (2- (2'-hydroxy-5'-methylphenyl) benzotriazole) can be used.

The ultraviolet light stabilizer may be contained in an amount of 0.1-2.5 parts by weight, preferably 0.3-2 parts by weight, based on 100 parts by weight of the acrylic resin syrup. When the ultraviolet light stabilizer is included within the above range, . When the ultraviolet light stabilizer is used in an amount less than the above range, the effect of preventing yellowing due to ultraviolet light irradiation is insufficient, and when the ultraviolet light stabilizer is used in an amount exceeding the above range, the initial color of the adhesive may turn yellow.

As the curing accelerator, known curing accelerators can be used, for example, N, N-bis- (2-hydroxyethyl) -p-toluidine, (NN-bis- (2-hydroxyethyl) Ethoxylate-toluidine) can be used.

The curing accelerator may be included in an amount of 0.1-5 parts by weight, preferably 0.1-3 parts by weight, based on 100 parts by weight of the acrylic resin syrup. If the amount is less than the above range, the curing reaction of the adhesive composition can not proceed at a good rate. If the amount exceeds the above range, the curing reaction of the adhesive composition proceeds too quickly and the storage stability of the composition decreases.

The coupling agent may be a known coupling agent, for example, silicate anhydride or the like. The coupling agent may be contained in an amount of 0.1-5 parts by weight, preferably 0.1-3 parts by weight, based on 100 parts by weight of the acrylic resin syrup. When the amount is less than the above range, the adhesive strength is lowered, and when it exceeds the above range, the physical properties of the adhesive and the coating property are lowered.

The curing agent may comprise 90-99.9 wt% plasticizer, 0.01-5 wt% initiator, and 0.01-5 wt% inorganic filler.

The plasticizer contained in the curing agent functions as a fusion solvent for imparting flexibility to a subject and improves the wettability of the adhesive to improve the bonding strength and dissolves the initiator in powder form to uniformize the reaction of the initiator. A benzoate system can be used. The dibenzoate-based plasticizer may be at least one selected from, for example, dipropylene glycol dibenzoate, diethylene glycol dibenzoate, polypropylene glycol dibenzoate, and polyethylene glycol dibenzoate.

The plasticizer may be contained in the curing agent in an amount of 90-99.9 wt%, preferably 95-99.5 wt%. If the amount is less than the above range, the initiator may not be sufficiently dissolved or precipitated at a low temperature. When the amount exceeds the above range, the adhesive strength and hardness are lowered and the curing time is delayed.

The initiator may be at least one selected from the group consisting of benzoyl peroxide, dibenzoyl peroxide, lauryl peroxide, acetyl peroxide and octyl peroxide. Preferably, the initiator is a benzoyl peroxide which is soluble in an organic solvent and can be generally used as a polymerization initiator of an acrylic resin syrup.

The initiator may be contained in the curing agent in an amount of 0.01-5 wt%, preferably 0.05-2 wt%. When the amount is less than the above range, the curing does not proceed and the adhesive strength is lowered. When the amount exceeds the above range, an unreacted initiator is present and workability is lowered.

The inorganic filler may be the same as the inorganic filler included in the subject, and it is preferable to use silica which has high rigidity to improve workability.

The inorganic filler may be contained in the curing agent in an amount of 0.01 to 5% by weight, preferably 0.05 to 3% by weight. When the amount is less than the above range, the workability is deteriorated and the price is increased. If it exceeds the above range, the workability is lowered and the adhesive strength is lowered.

The adhesive composition for artificial marble of the present invention may optionally contain at least one selected from the group consisting of a melt strength enhancer, a lubricant, an antistatic agent, an antioxidant, a colorant, an antioxidant, a dispersant, The kind and content thereof are not particularly limited.

The adhesive composition for artificial marble of the present invention as described above can be produced by the following method.

First, an acrylic resin syrup is prepared by mixing 15-50 wt% of polymethyl methacrylate and 50-85 wt% of methyl methacrylate. 0.1-5 parts by weight of a crosslinking agent, 0.05-5 parts by weight of a plasticizer, 0.01-0.8 parts by weight of a thiol-based polymerization retarder and 0.1-10 parts by weight of an additive are added to 100 parts by weight of the obtained acrylic resin syrup, 1-25 parts by weight of a filler is added and dispersed for 2-30 minutes to prepare a subject.

0.01 to 5% by weight of an initiator is dissolved in 90 to 99.9% by weight of a plasticizer, and 0.01 to 5% by weight of an inorganic filler is added and dispersed.

The adhesive and the hardener are mixed in a volume ratio of 12: 1 to 8: 3 to obtain an adhesive composition for artificial marble.

Here, the viscosity before mixing with the curing agent and before curing may be 1500-4000 cps, preferably 2000-3500 cps, at a temperature of 20-25 캜. When the amount is less than the above range, the workability of the adhesive deteriorates, and when it exceeds the above range, the application amount of the adhesive decreases.

The adhesive composition for artificial marble of the present invention contains a specific amount of a thiol-based polymerization retarder and has an excellent light fastness, good initial color of the adhesive, and satisfactory adhesion strength required.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.

[Example]

1. Adhesive composition for artificial marble

The composition of the adhesive for artificial marble according to the preferred embodiment of the present invention is shown in Table 1 below.

- The weight ratio of polymethylmethacrylate and methylmethacrylate in the production of acrylic resin syrup was 34:66.

The following composition and the curing agent were mixed in a volume ratio of 10: 1.

2. Comparison of light fastness, adhesive strength, adhesive initial color of artificial marble adhesive

The components of Table 1 were mixed to prepare an adhesive for artificial marble, and the light resistance and adhesive strength were measured. The results are shown in Table 2 below.

- Light resistance was measured by the following method.

1) The adhesives of Examples 1-4 and Comparative Example 1-2 prepared above were coated on a slide glass in a size of 76x26 mm and cured.

2) The L (brightness), a * (+ a *, b *, and b * values of the cured adhesive) Measure using a system.

3) After leaving for 200 hours in a QUV test machine of 340nm, measure L, a, b value and calculate ΔE (color difference value) based on this.

- Adhesive strength was evaluated by applying the adhesives of Examples 1-4 and Comparative Example 1-2 prepared above to a specimen of 65 ⅹ 12.5 ⅹ 12.5 mm, then sticking to the same size specimen, And the strength at the time when the specimen was broken was measured by pressing the adhesive portion at a speed of 1 mm / min.

- The initial color of the adhesive was measured by using a colorimeter to measure the b * value of the yellow color. The bigger the b * value, the more yellowish it is.

Example Comparative Example One 2 3 4 One 2 3 Light fastness (? E) 3.03 2.59 3.64 3.15 4.32 2.05 2.12 Adhesion strength (kgf / mm ² ) 8.73 8.48 8.32 8.24 9.04 5.42 5.61 Adhesive Initial Color (b *) 2.97 3.02 3.03 3.21 3.13 3.22 5.03

As shown in Table 2, the light resistance of Example 1-4 according to the present invention is superior to that of Comparative Example 1, which does not include the thiol-based polymerization retarder, and satisfies the required adhesive strength.

On the other hand, Comparative Example 2 containing an excessive amount of the thiol-based polymerization retarder showed better light fastness than Example 1-4, but the bonding strength was very low and the required bonding strength was not satisfied.

In Comparative Example 3 containing an excessive amount of ultraviolet stabilizer, the light fastness was excellent, but the initial color of the adhesive turned yellow, and it was found that the joint of the adhesive portion did not appear smooth during the artificial marble bonding process.

Claims (14)

A subject comprising 0.01-0.8 parts by weight of a thiol-based polymerization retarder based on 100 parts by weight of an acrylic resin syrup; And curing agents; And an adhesive agent for artificial marble. The method according to claim 1,
Wherein the acrylic resin syrup is a mixture of polymethyl methacrylate (A) and acrylic monomer (B). 3. The method of claim 2,
Wherein the polymethyl methacrylate (A) is contained in the acrylic resin syrup at 15-50 wt%. 3. The method of claim 2,
Wherein the acrylic monomer (B) is contained in the acrylic resin syrup in an amount of 50-85 wt%. The method according to claim 1,
Wherein the thiol-based polymerization retarder is at least one selected from the group consisting of a monofunctional thiol-based polymerization retarder and a multifunctional thiol-based polymerization retarder. The method according to claim 1,
Wherein the thiol-based polymerization retarder is selected from the group consisting of n-butyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and t-butyl mercaptan Wherein the adhesive composition is at least one of the following. The method according to claim 1,
Wherein the thiol-based polymerization retarding agent is an organic compound containing 4 to 12 carbon atoms of a thiol group. The method according to claim 1,
The subject matter further comprises at least one inorganic filler selected from the group consisting of aluminum trihydroxide, mica, talc, clay, calcium carbonate and silica having a size of 0.5-5 mu m. . 9. The method of claim 8,
Wherein the inorganic filler is contained in an amount of 1-25 parts by weight, preferably 5-20 parts by weight, based on 100 parts by weight of the acrylic resin syrup. The method according to claim 1,
Wherein the subject further comprises a cross-linking agent. 11. The method of claim 10,
Wherein the crosslinking agent is contained in an amount of 0.1-5 parts by weight based on 100 parts by weight of the acrylic resin syrup. The method according to claim 1,
Wherein the subject matter further comprises 0.05 to 5 parts by weight of a plasticizer based on 100 parts by weight of the acrylic resin syrup. The method according to claim 1,
Wherein the subject matter further comprises 0.1-2.5 parts by weight of an ultraviolet light stabilizer per 100 parts by weight of the acrylic resin syrup. The method according to claim 1,
Wherein the curing agent comprises 90-99.9 wt% plasticizer, 0.01-5 wt% initiator, and 0.01-5 wt% inorganic filler.