KR100413747B1 - Silicon-crosslinked resin composition having excellent impact resistance and anti-fouling property - Google Patents

Abstract

PURPOSE: Provided is a resin composition comprising at least one modified acryl monomer having excellent weatherability and impact resistance and hydrolyzable silyl group per molecule at end or side chain of resin. CONSTITUTION: The composition comprises: a copolymer A represented by formula I; a curing catalyst B which is a mixture of component B1 selected from the group consisting of organic titanate compound, organic tin compound, acidic phosphate ester compound, amine compound, and a mixture thereof, and component B2 represented by formula II; and a hydrolyzable compound C. In the formulas, R1 is hydrogen or methyl group, or C1-C20 alkyl or aryl group, which may comprise non-metal elements of group V, VI, or VII of periodic table as substituent, X1 is C1-C20 alkyl or aryl group which may comprise non-metal elements of group V, VI, or VII of periodic table as substituent, R4 is divalent alkylene or arylene group of C1-C10 which may comprise non-metal elements of group V, VI, or VII of periodic table as substituent, R5 is C1-C10 alkyl or aryl group which may comprise non-metal elements of group V, VI, or VII of periodic table as substituent, Y is halogen, hydroxyl group, alkoxy group, acyloxy group, aminoxy group, phenoxy group, thioalkoxy group, or alkenyloxy group, R7, R8, and R9 are methyl or C1-C13 alkyl or aryl group, which may comprise non-metal elements of group V, VI, or VII of periodic table as substituent, p, q, and r vary according to the amount of each component used, l is 0 or 1, m1 is an integer of 0, or 1-10, m2 is an integer of 1-30, and n is an integer of 0, or 1-2.

Description

Silicone crosslinkable resin composition excellent in impact resistance and stain resistance

The present invention relates to a silicone crosslinkable resin composition having excellent impact resistance and fouling resistance, and more particularly, one hydrolyzable silyl group and a modified acrylic monomer having excellent weather resistance and impact resistance at one end or side chain of the resin. It relates to the resin composition contained above.

The paint can be divided into its functions, which can be roughly divided into protective and decorative materials. The characteristics of the paint for protecting the body include weather resistance, impact resistance, rust resistance, water resistance, chemical resistance, and the like. The holding power, color holding power, and stain resistance can be cited. In general, the protective material for the body is mainly used in steel structures such as bridges, containers, ships, etc., and decorative paint is mainly used for exterior walls, furniture, and the like.

However, in the field of outdoor structures, containers, ships, bridges, etc., the importance of aesthetics and pollution resistance as well as basic protection functions such as chemical resistance and rust prevention is increasing. In other words, the functional trend is becoming complex.

In general, acrylic resins are used for various purposes due to their excellent weatherability and surface properties. Water-soluble acrylic resins are not widely used until now due to severe ups and downs of physical property changes depending on the coating method and the surrounding environment at the time of coating. Due to the toxicity of the group, there are restrictions on use, and epoxy-modified acrylic resins have problems in terms of glossiness retention. Recently, silicone cross-linked acrylic resins have been in the spotlight.

Resin obtained by introducing and copolymerizing a silane coupling agent into an acrylic main chain based on an acrylic monomer as a main component has recently been applied to a variety of applications (Japanese Patent Publication No. Hei 64-75567, etc.). By crosslinking at room temperature to form a dense network structure there is an advantage in coating properties such as solvent resistance, chemical resistance and adhesion to inorganic substrates, but has a disadvantage of weak impact resistance.

In general, there are three methods for modifying impact resistance in coating resins. The first method is to synthesize a resin using a monomer having a low glass transition temperature in order to provide flexibility, which is difficult to achieve satisfactory effects in a thermosetting resin. The second method is a method of imparting a plasticizer to the resin. In Japanese Patent Laid-Open No. 55-152745, a method of blending a diallyl phthalate-based polymer with a silyl group-containing vinyl polymer is used. Since they are not combined with the main chain of the resin and are simply mixed, they are damaged when they are exposed to the outdoors, and thus there is a disadvantage in that they cannot guarantee long-term durability. Third, there is a method of introducing an internal plasticizer into the resin itself, and by modifying a plasticizer or liquid rubber having an impact-modifying effect and copolymerizing it with other monomers, the effect can be maximized by appropriate selection of the internal plasticizer.

The present inventors studied a method of reinforcing impact resistance by introducing a rubber-modified acrylic monomer, a polysulfide-modified acrylic monomer, or the like into the acrylic main chain containing a hydrolyzable silyl group to improve impact resistance using the third method described above. However, the storage stability was poor in the synthesis of the resin and in the preparation of the paint using the same, and in the case of the formed coating film, the physical properties were deteriorated in weather resistance and gloss.

Accordingly, the present inventors select a curing agent and an appropriate internal plasticizer in which the reaction structure is adjusted based on a known fact that not only the resin but also the physical properties of the cured coating film are affected by the composition and the amount of the curing catalyst. By using it, the silicone crosslinkable resin composition excellent in impact resistance and stain resistance was developed.

That is, the present invention is capable of room temperature or heat curing by moisture and curing accelerators in the air, and excellent in weather resistance, chemical resistance, adhesion, corrosion resistance, and storage stability, and in particular, silicone crosslink type having excellent impact resistance and stain resistance. The purpose is to provide a resin composition.

Hereinafter, the present invention will be described in more detail.

The composition of this invention consists of copolymer A represented by the following general formula (I), a curing catalyst B, and a hydrolysable compound C.

In formula (I),

R ₁ is hydrogen or a methyl group,

As an alkyl or aryl group having 1 to 20 carbon atoms, a nonmetallic element of Group V, VI or VII on the periodic table may be included as a substituent,

X ₁ is an alkyl or aryl group having ₁ to 20 carbon atoms and may include a nonmetallic element of Group V, VI or VII on the periodic table as a substituent,

R ₄ is a divalent alkylene or arylene group having 1 to 10 carbon atoms, and may include a substituent of a nonmetallic element of Group V, VI, or VII on the periodic table.

R ₅ is an alkyl or aryl group having 1 to 10 carbon atoms and may include a nonmetallic element of Group V, VI or VII on the periodic table as a substituent,

Y is a halogen, a hydroxy group, an alkoxy group, an aoxyoxy group, an amino group, a phenoxy group, a thioalkoxy group, or an alkenyloxy group,

p, q, and r are amounts that change depending on the amount of each component used,

l is 0 or 1,

m ₁ is an integer between 0 or 1-10,

m ₂ is an integer from 1-30,

n is an integer between 0 or 1-2.

The curing catalyst B is a mixture of component B1 and component B2 represented by the following general formula (II), wherein component B1 is an organic titanate compound, an organic chitin compound, an acidic phosphate ester compound, an amine compound and one or more thereof. 2 or more types of mixtures, etc. are mentioned.

In formula (II),

Y is a halogen, a hydroxy group, an alkoxy group, an aoxyoxy group, an amino group, a phenoxy group, a thioalkoxy group, an alkenyloxy group,

R ₇ , R ₈ and R ₉ may be a methyl group or an alkyl or aryl group having 1 to 13 carbon atoms and may include a nonmetallic element of Group V, VI or VII on the periodic table as a substituent.

n is an integer between 0 or 1-2,

m2 is an integer between 1-30,

R ₅ is an alkyl or aryl group having 1 to 10 carbon atoms and may include a substituent of a nonmetallic element of Group V, VI or VII on the periodic table.

Copolymer A represented by the general formula (I) is one or two or more compounds of the component A1 represented by the following general formula (I-1) and a component represented by the following general formula (I-2). One or two or more compounds of A2 and one or two or more compounds of component A3 represented by the following general formula (I-3) can be obtained by radical copolymerization.

In the formulas (I-1), (I-2) and (I-3),

R ₁ is hydrogen or a methyl group,

As an alkyl or aryl group having 1 to 20 carbon atoms, a nonmetallic element of Group V, VI or VII on the periodic table may be included as a substituent,

X ₁ is an alkyl or aryl group having ₁ to 20 carbon atoms and may include a nonmetallic element of Group V, VI or VII on the periodic table as a substituent,

R ₄ is a divalent alkylene or arylene group having 1 to 10 carbon atoms, and may include a substituent of a nonmetallic element of Group V, VI, or VII on the periodic table.

R ₅ is an alkyl or aryl group having 1 to 10 carbon atoms and may include a nonmetallic element of Group V, VI or VII on the periodic table as a substituent,

Y is a halogen, a hydroxy group, an alkoxy group, an aoxyoxy group, an amino group, a phenoxy group, a thioalkoxy group, or an alkenyloxy group,

l is 0 or 1,

m ₁ is an integer between 0 or 1-10,

m ₂ is an integer from 1-30,

n is an integer between 0 or 1-2.

The component Al represented by the above general formula (I-1) is used for the purpose of maintaining the main chain of the copolymer, and is generally used as an excellent acrylic monomer having excellent reactivity, such as methyl methacrylate and methyl acrylate. , Ethyl acrylate, ethyl methacrylate, butyl methacrylate, butyl acrylate, isobutyl methacrylate, isobutyl acrylate, 2-hydroxyethyl methacrylate, styrene, alpha-methylstyrene, methoxyethyl acryl The rate etc., but this example is not limited to this.

Component A2 represented by the above general formula (I-2) is introduced into the end or side chain of the copolymer of the present invention to control the crosslinking density, such as gloss, weather resistance, fouling resistance, adhesion to inorganic materials, water resistance, and the like. It is used for improvement, and specific examples thereof

Etc., but this example is not limited thereto.

Component A3 represented by the above general formula (I-3) is a compound which is introduced into the copolymer of the present invention and serves as an internal plasticizer for imparting the effect of impact reinforcement, and is synthesized by the following reaction.

In the above components A3-1 and A3-2,

R ₁ is hydrogen or a methyl group,

m2 is an integer between 1 and 30.

Component A3 synthesized as described above may have a variety of structures depending on the type of monomer used in the synthesis, and contains a reactive double bond at one end to facilitate copolymerization with other acrylic monomers and in the main chain of the resin during copolymerization. It is introduced to reinforce the impact in the long term.

Specific examples of the component A3-1 include glycidyl methacrylate, glycidyl acrylate, and the like, and specific examples of the component A3-2 include polypropylene glycol (PPOL), and the like. It does not limit the scope of the invention.

The curing catalyst B is a component that plays an important role in producing a coating film having a stable siloxane bond by actively carrying out the hydrolysis and condensation reaction of the copolymer A of the present invention in the presence of moisture in the air.

In the composition of the present invention, the curing catalyst B is composed of a mixture of component B1 and component B2 represented by the above general formula (II), and component B1 is an organotitanate compound, an organic tin compound, an acidic phosphate ester compound, an amine compound and these 1 type, or 2 or more types of mixtures, etc. are mentioned.

Examples of the organotitanate compound include tetrabutyl titanate, tetraisopropyl titanate, and the like. Examples of the organic tin compound include dibutyltin dilaurate, tin octoate, dibutyltin phthalate, and the like. Examples of the phosphate ester compound include bis (2-ethylhexyl) phosphoric acid, diisodecyl phosphoric acid and dimethyl phosphoric acid. Examples of the amine compound include organic amines generally used as epoxy curing agents, Polyamides, amino group-containing organic silanes, reactants of amines and epoxy resins; and the like, but the present example is not limited thereto.

Component B2 represented by the general formula (II) is synthesized by the following reaction.

Where

Y is a halogen, a hydroxy group, an alkoxy group, an aoxyoxy group, an amino group, a phenoxy group, a thioalkoxy group, or an alkenyloxy group,

R ₇ , R ₈ and R ₉ may be a methyl group or an alkyl or aryl group having 1 to 13 carbon atoms and may include a nonmetallic element of Group V, VI or VII on the periodic table as a substituent.

n is an integer between 0 or 1-2,

m2 is an integer between 1-30,

R ₅ is an alkyl or aryl group having 1 to 10 carbon atoms and may include a substituent of a nonmetallic element of Group V, VI or VII on the periodic table.

Examples of the component B2-1 include CARDURA E10 of SHELL, etc. Examples of the component B2-2 include JEFFAMINE D 230, 400, 2000, etc. of TEXACO, and examples of the component B2-3. Glycidoxypropyl trimethoxysilane, -Glycidoxypropyl methyl dimethoxy silane and the like, but this example is not limited thereto.

The hydrolyzable compound C in the composition of the present invention is a component used to improve storage stability mainly in synthesizing and storing Copolymer A of the present invention or in preparing a paint using Copolymer A of the present invention. Is hydrolysable organic compound alone, such as triethoxy methane, trimethoxy ethane, triethyl ortho acetate, or hydrolysable silicon compounds such as ethyl silicate, methyltrimethoxysilane, methyltriethoxysilane alone, or the hydrolyzable The organic compound and the hydrolyzable silicone compound may be one kind or a mixture of two or more kinds thereof. Among them, ethyl silicate is a compound capable of crosslinking reaction with the copolymer A of the present invention when forming a cured coating film, and the surface hardness of the cured coating film. And it can contribute to the improvement of physical properties.

The silicone crosslinkable resin composition excellent in impact resistance and fouling resistance of the present invention is composed of Copolymer A, a curing catalyst B, and a hydrolyzable compound C, the amount of which is used based on 100 parts by weight of the copolymer A, 0.5 to 40 parts by weight, preferably 1 to 30 parts by weight are suitable, and 5 to 50 parts by weight, preferably 5 to 45 parts by weight of the hydrolyzable compound C is suitable.

In the composition of the present invention, copolymer A is synthesized with components A1, A2, and A3, and component A1 is a component constituting the main chain of copolymer A, and 20 to 80 parts by weight is suitable for 100 parts by weight of copolymer A, If it is less than 20 parts by weight, the durability of the coating film is lowered, and if it is more than 80 parts by weight, the coating film is too hard, the impact falls or the glossiness holding power is low.

Component A2 is 5 to 50 parts by weight with respect to 100 parts by weight of copolymer A as a main part of controlling the crosslinking density of copolymer A, and when it is less than 5 parts by weight, the crosslinking density of the coating film is too low, resulting in chemical resistance and water resistance, If the glossiness holding power is poor, and if it exceeds 50 parts by weight, the crosslinking density of the coating film becomes too high and the internal stress is increased, so that the adhesion to the inorganic material is poor.

Component A3 is a suitably modified impact modifier for improving impact resistance, and is suitable for 5 to 50 parts by weight, and if it is less than 5 parts by weight, it does not have a great effect on improving the impact resistance of the coating film. Too high viscosity results in poor workability and poor solubility in solvents and poor gloss retention.

Component A3 is an impact modifier produced by reacting components A3-1 and A3-2 with a suitable ratio of 1: 1.2 of component A3-1 to component A3-2.

The method of preparing Copolymer A in the composition of the present invention may be emulsion polymerization, block polymerization or solution polymerization, among which solution polymerization is suitable, and as a radical initiator, azo compounds such as azobisisobutyronitrile or benzoyl peroxide Peroxides, such as these, can be used individually or in mixture.

The solids content of copolymer A in the composition of the present invention is 30 to 70 parts by weight is suitable, and the solvent used is non-reactive solvents such as hydrocarbons such as xylene, toluene and acetates such as ethyl acetate, butyl acetate or ketone alcohols. May be used alone or in combination.

The reaction temperature at the time of polymerizing copolymer A in the composition of the present invention is suitably in the range of 60 to 130 ° C., and the amount of the initiator is preferably 0.5 to 5% by weight based on 100 parts by weight of the copolymer A. And the weight average molecular weight of copolymer A has the preferable range of 5,000-100,000. If the weight average molecular weight of copolymer A is less than 5,000, the durability of a coating film will fall, and if it exceeds 100,000, the viscosity of a copolymer will become too high and workability will become poor.

In the composition of the present invention, the curing catalyst B is composed of a mixture of component B1 and component B2, and a composition ratio of component B1 to B2 is preferably in a ratio of 10 to 90 to 90 to 10 as a solid content. Component B2 is a compound produced by the reaction of components B2-1, B2-2 and B2-3, and the weight average molecular weight of component B2 is preferably in the range of 500 to 10,000. If the weight average molecular weight is less than 500, the impact reinforcing effect is insignificant, and if it exceeds 10,000, the crosslinking reaction rate becomes slow.

The following Preparation Examples, Examples and Comparative Examples will be described in more detail the manufacturing method, efficacy, and effect of the silicone cross-linked resin composition excellent in impact resistance and contamination resistance according to the present invention to limit the scope of the present invention no.

Preparation Example 1 Preparation of Component A3

Into a 1 liter four-necked round flask equipped with a cooling device, a condenser, and a nitrogen input device, 525 parts by weight of polypropylene glycol (Korea Polyol, PPG-1000) was added thereto, and the temperature was raised to 140 ° C. while stirring. When the reaction temperature is kept constant, 75 parts by weight of glycidyl methacrylate is continuously injected into the flask for about 30 minutes. After all the glycidyl methacrylate was injected, the reaction was carried out for 3 hours, and then, after completion of the reaction after measuring the epoxy equivalent weight and IR analysis at 1 hour interval, the reaction temperature was lowered to 80 ° C, and 150 parts by weight of xylene was added. Terminate Solids content of the product is 79-80%.

Preparation Example 2-3 Preparation of Component A3

Synthesis according to the method of Preparation Example 1, in the case of Preparation Example 2 559.8 parts by weight of polypropylene glycol (Korean polyol, PPG-2000), 40.2 parts by weight of glycidyl methacrylate, 150 parts by weight of xylene was used, Preparation Example 3 In the case of 573 parts by weight of polypropylene glycol (Korea Polyol, PPG-3000), 27 parts by weight of glycidyl methacrylate, 150 parts by weight of xylene are used.

Solid content of the manufacture examples 2 and 3 is 79-80%.

Preparation Example 4-6 and Comparative Preparation Example 7-9: Preparation of Copolymer A

In a 0.3 liter four-necked flask equipped with a cooling device, a condenser and a nitrogen input device, solvent A of 1 was added as described in Table 1 below, nitrogen was added and stirred, and the temperature was increased as described in Table 1.

After the temperature is kept constant, the monomers and initiators of 2 are mixed well as described in Table 1, and placed in a dropping device, and the dropping device is adjusted dropwise at a constant rate for 3 hours. After completion of the dropwise addition, the holding reaction is carried out for 1 hour, and the solvent B of 3 and the initiator are mixed well, and the mixture is added to the dropping apparatus. The reaction is terminated after 1 hour in which both the solution B of the solvent 3 and the initiator are added dropwise to obtain a copolymer having the properties shown in Table 1.

Table 1. Preparation of Copolymer A

Preparation Example 10 Preparation of B2 Component

After adding nitrogen to a 1 liter four-necked flask equipped with a cooling device, a condenser and a nitrogen input device, 400 parts by weight of JEFFAMINE D 400 from TEXACO Inc. was heated to 40 ° C. After constant injection for 2 minutes to 2 hours, the reaction is confirmed by IR or wet test every 30 minutes or 1 hour to obtain the product. 330 parts by weight of this product and 131 parts by weight of glycidoxypropyl trimethoxy silane is placed in a 1 liter four-necked flask and the reaction temperature is raised to 80 ° C., after which the reaction product is maintained for 3 hours to obtain product B2.

Example 1-4 and Comparative Example 5-6: Preparation of Paint

Preparation of the paint 1-4 was carried out using the amounts shown in Table 2 below in the copolymer A of Preparation Example 4-6 and Comparative Preparation Example 7-9 to the titanium A, xylene, trimethyl ortho acetate as a hydrolyzable compound, Put a UV absorber, glass beads, etc. to disperse well for 1 to 2 hours with a disperser to prepare a paint. If necessary, additives such as a dispersant may be further used.

Table 2. Paint Manufacturing

Table 3. Coating Property Test Results

DP8R; DAIHACHI CHEMICAL (Japan) Products

KBM 403; SIINETSU (Japan) Products

* 2 ; Curing agent in which the curing catalyst 1 and the product of Preparation Example 10 are mixed in a weight ratio of 1/1 in a solid state

* 3; Curing agent in which the curing catalyst 1 and the product of Preparation Example 10 are mixed at a weight ratio of 1 / 0.5 in a solid state

* 4 ; Curing agent obtained by mixing the curing catalyst 1 and the product of Preparation Example 10 in a weight ratio of 1 / 0.3 of the solid state

* 5; Use of QUV / SE models from THE Q-PANEL COMPANY (USA)

* 6; Test by ASTM D2794-84 Method

(Excellent; 5-4-3-2-1; poor)

* 7; Aqueous solution containing 0.1% carbon black and 1% sulfuric acid was prepared, sprayed onto the coating film, and the process of BAKING at DRY OVEN at 60 ℃ for 20 minutes was performed twice in succession. box

(G; Good, A; Normal, P; Poor)

As can be seen from the coating properties test results of Table 3, it can be seen that the composition of the present invention is excellent in gloss retention, impact resistance, and stain resistance.

Claims (5)

Component B1 selected from copolymer A represented by the following general formula (I), an organic titanate compound, an organic chitin compound, an acidic phosphate ester compound, an amine compound and one or two or more thereof, and the following general formula (II) A silicone crosslinkable resin composition excellent in impact resistance and fouling resistance, comprising a curing catalyst B which is a mixture of component B2 represented by the formula (I) and a hydrolyzable compound C. In the formulas (I) and (II), R ₁ is hydrogen or a methyl group, As an alkyl or aryl group having 1 to 20 carbon atoms, a nonmetallic element of Group V, VI or VII on the periodic table may be included as a substituent, X ₁ is an alkyl or aryl group having ₁ to 20 carbon atoms and may include a nonmetallic element of Group V, VI or VII on the periodic table as a substituent, R ₄ is a divalent alkylene or arylene group having 1 to 10 carbon atoms, and may include a substituent of a nonmetallic element of Group V, VI, or VII on the periodic table. R ₅ is an alkyl or aryl group having 1 to 10 carbon atoms and may include a nonmetallic element of Group V, VI or VII on the periodic table as a substituent, Y is a halogen, a hydroxy group, an alkoxy group, an aoxyoxy group, an amino group, a phenoxy group, a thioalkoxy group, or an alkenyloxy group, R ₇ , R ₈ and R ₉ may be a methyl group or an alkyl or aryl group having 1 to 13 carbon atoms and may include a nonmetallic element of Group V, VI or VII on the periodic table as a substituent. p, q, and r are amounts that change depending on the amount of each component used, l is 0 or 1, m ₁ is an integer between 0 or 1-10, m ₂ is an integer from 1-30, n is an integer between 0 or 1-2. The silicone crosslinkable resin composition according to claim 1, comprising 0.5 to 40 parts by weight of a curing catalyst B and 5 to 50 parts by weight of a hydrolyzable compound C with respect to 100 parts by weight of the copolymer A. The said copolymer A is 20-80 weight part of components A1 represented by the following general formula (I-1), and 5-50 weight part of components A2 represented by the following general formula (I-2). And 5 to 50 parts by weight of component A3 represented by the following General Formula (I-3) by radical copolymerization. In the formulas (I-1), (I-2), and (I-3), R ₁ is hydrogen or a methyl group, As an alkyl or aryl group having 1 to 20 carbon atoms, a nonmetallic element of Group V, VI or VII on the periodic table may be included as a substituent, X ₁ is an alkyl or aryl group having ₁ to 20 carbon atoms and may include a nonmetallic element of Group V, VI or VII on the periodic table as a substituent, R ₄ is a divalent alkylene or arylene group having 1 to 10 carbon atoms, and may include a substituent of a nonmetallic element of Group V, VI, or VII on the periodic table. R ₅ is an alkyl or aryl group having 1 to 10 carbon atoms and may include a nonmetallic element of Group V, VI or VII on the periodic table as a substituent, Y is a halogen, a hydroxy group, an alkoxy group, an aoxyoxy group, an amino group, a phenoxy group, a thioalkoxy group, or an alkenyloxy group, l is 0 or 1, m ₁ is an integer between 0 or 1-10, m ₂ is an integer from 1-30, n is an integer between 0 or 1-2. The silicone crosslinkable resin composition according to claim 3, wherein the component A3 represented by the general formula (I-3) is produced by reacting the following component A3-1 with the following component A3-2. In the above components A3-1 and A3-2, R ₁ is hydrogen or a methyl group, m2 is an integer between 1 and 30. The hydrolyzable compound C according to claim 1 or 2, wherein the hydrolyzable compound C is a hydrolyzable organic compound alone, such as triethoxymethane, trimethoxy ethane, triethyl ortho acetate, trimethyl ortho acetate, or ethyl silicate or methyltrimethoxy silane. And a hydrolyzable silicone compound such as methyltriethoxy silane alone or one or two or more mixtures of the hydrolyzable organic compound and the hydrolyzable silicone compound, respectively.