JP5610279B2 - Moisture curable sealant with excellent paint adhesion - Google Patents

Description

  The present invention relates to a moisture curable sealing material having excellent adhesion between a sealing material and a paint when the surface of the sealing material is painted. Further, the present invention relates to a moisture curable sealing material that is excellent in water-resistant adhesion in addition to paint adhesion.

Polyoxyalkylene polymer having a crosslinkable silicon group (hereinafter simply referred to as a crosslinkable silicon group) having a hydroxyl group or hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond with moisture. Is disclosed in Patent Document 1. This polymer is also manufactured and sold by Kaneka Corporation under the trade name of MS polymer. A typical example of the polyoxyalkylene polymer having a crosslinkable silicon group is the following polymer having a methyldimethoxysilyl group as a crosslinkable silicon group at the end of the polyoxypropylene polymer chain.

_{CH 3 (CH 3 O) 2} Si~~~ ( polyoxypropylene _{chain) ~ (OCH 3) 2 CH} 3

  Since this polymer is usually liquid, it can be applied to a substrate and can be filled into a gap or a mold. If left as it is after coating and filling, the polymer undergoes a hydrolysis reaction and a silanol condensation reaction due to moisture in the air, and the polymers are cross-linked by a siloxane bond to usually produce a rubber-like cured product. Because of such characteristics, the polyoxyalkylene polymer having a crosslinkable silicon group is used as a sealing material called a modified silicone sealing material, and is particularly useful as a building sealing material.

  The surface of the sealing material may be painted. In particular, when a sealing material is used for a joint of a wall material such as a siding board and the surface of the wall material is painted, the sealing material for the joint is often painted at the same time. The modified silicone sealant is superior in adhesion of the paint to the surface of the sealant compared to the silicone sealant, but it is desired to further improve the adhesion of the paint.

  Patent Document 1 discloses that the adhesion of a coating can be improved by adding a (poly) alkylene oxide ester of (meth) acrylic acid to a modified silicone sealant composition. Patent Documents 2 to 6 disclose that adhesion of a coating can be improved by adding a silicon compound or the like having an amino group or a group capable of generating an amino group to the modified silicone sealant composition. Patent Document 7 discloses that the adhesion of a coating can be improved by adding an alkylarylsulfonamide to the modified silicone sealant composition.

  Patent Document 8 discloses that the adhesion of a coating can be improved by adding a reaction product of an aminosilane compound and an isocyanate compound to a modified silicone sealant composition. Patent Document 9 discloses that the adhesion of a paint can be improved by using a polyoxyalkylene polymer having a specific amount of crosslinkable silicon groups as a modified silicone sealant. Patent Document 10 discloses that the adhesion of a paint can be improved by adding a (meth) acrylic acid ester polymer using a metallocene compound as a polymerization catalyst.

Japanese Patent Laid-Open No. 06-220315 JP 09-299874 A Japanese Patent Laid-Open No. 09-302213 Japanese Unexamined Patent Publication No. 09-310015 Japanese Patent Laid-Open No. 10-168299 JP 2007-314727 A JP 2002-146216 A JP 2004-075836 A Japanese Patent Laying-Open No. 2005-082681 JP 2008-019300 A JP 2008-174611 A JP 2008-239809 A

  An object of the present invention is to provide a sealing material containing a polyoxyalkylene polymer having a crosslinkable silicon group and having excellent paint adhesion.

  Patent Documents 11 to 12 disclose a curable composition containing a polyoxyalkylene polymer having a crosslinkable silicon group and a metal chelate compound of an alkylphenol resin as a tackifier resin, and this composition is a pressure sensitive adhesive or an adhesive. It has been found that it is excellent in heat-resistant creep resistance and heat-resistant adhesion, and it is possible to improve recyclability without leaving glue on the adherend when it is peeled off from the adherend. The present inventors have found that when this composition is used for a sealing material, particularly an architectural sealing material specified in JIS A5758, the paint adhesion on the surface of the sealing material is excellent, leading to the present invention. In addition, since the composition of patent documents 11-12 is mainly used as an adhesive or an adhesive agent, the metal chelate compound of the alkylphenol resin used as tackifying resin is 50 weight part or more with respect to 100 weight part of polymers. In the present invention, the amount of the metal chelate compound of the alkylphenol resin is within a relatively small range of 50 parts by weight or less with respect to 100 parts by weight of the polymer. Specifically, the present invention is the following sealing material.

Claim 1:
(A) 100 parts by weight of a polyoxyalkylene polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having a crosslinkable silicon group that can be crosslinked by forming a siloxane bond with moisture, (B) A moisture-curable sealant containing 1 to 10 parts by weight of a chelate compound comprising an alkylphenol resin and a metal oxide and / or metal hydroxide.

Claim 2:
The crosslinkable silicon group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond with moisture is a crosslinkable silicon group represented by the formula (1). The moisture-curable sealing material according to claim 1.

(In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or R ¹ ₃ SiO— (R ¹ is the same as above), and when two or more R ¹ are present, they may be the same or different, and X is a hydroxyl group or a hydrolyzable group. Represents a group, and when two or more X are present, they may be the same or different, a represents 0, 1, 2 or 3, b represents 0, 1 or 2; And n formulas (2):

におけるｂは同一である必要はない。ｎは０〜１９の整数を示す。但し、ａ＋（ｂの和）≧１を満足するものとする。）

B in need not be the same. n shows the integer of 0-19. However, a + (sum of b) ≧ 1 is satisfied. )

Claim 3:
The moisture-curable sealing material according to claim 2, wherein the crosslinkable silicon group represented by the formula (1) is a crosslinkable silicon group represented by the formula (3).

（式中、Ｒ^１，Ｘ，ａは前記と同じ）

(Wherein R ¹ , X and a are the same as above)

Claim 4:
The moisture-curable sealing material according to any one of claims 1 to 3, wherein the hydrolyzable group is an alkoxy group in the crosslinkable silicon group.

Claim 5:
The moisture-curable sealing material according to claim 4, wherein the hydrolyzable group is a methoxy group.

Claim 6:
The moisture curable sealant according to any one of claims 1 to 5, wherein the polyoxyalkylene polymer is a polyoxypropylene polymer.

Claim 7:
Further, (C) a (meth) acrylic acid ester-based polymer having a hydroxyl group or hydrolyzable group bonded to a silicon atom and having a crosslinkable silicon group that can be crosslinked by forming a siloxane bond with moisture (A) ) 20 to 100 with respect to 100 parts by weight of a polyoxyalkylene polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having a crosslinkable silicon group that can be crosslinked by forming a siloxane bond with moisture. The moisture-curable sealing material according to any one of claims 1 to 6, comprising a part by weight.

Claim 8:
(B) A chelate compound consists of a t-butylphenol resin and magnesium oxide, The moisture hardening sealing material of any one of Claims 1-7 characterized by the above-mentioned.

Claim 9:
Furthermore, (D) the curing catalyst (A) a polyoxyalkylene polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having a crosslinkable silicon group that can be crosslinked by forming a siloxane bond with moisture. The moisture-curable sealing material according to any one of claims 1 to 8, comprising 0.5 to 10 parts by weight with respect to 100 parts by weight.

Claim 10:
The moisture curable sealant according to any one of claims 1 to 9, wherein the sealant is a building sealant.

  The sealing material containing a polyoxyalkylene polymer having a crosslinkable silicon group according to the present invention contains an alkylphenol resin and a chelate compound comprising a metal oxide and / or a metal hydroxide, so that the surface of the cured sealing material is cured. When painted, it has excellent paint adhesion. Moreover, it has the effect which is excellent in the water-resistant adhesiveness with respect to a base material which is an important property as a sealing material for buildings.

  In the present invention, a crosslinkable silicon group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond with moisture is known, and a typical example is represented by the formula (1) And a group represented by

(In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or R ¹ ₃ SiO— (R ¹ is the same as above), and when two or more R ¹ are present, they may be the same or different, and X is a hydroxyl group or a hydrolyzable group. Represents a group, and when two or more X are present, they may be the same or different, a represents 0, 1, 2 or 3, b represents 0, 1 or 2; And n formulas (2):

におけるｂは同一である必要はない。ｎは０〜１９の整数を示す。但し、ａ＋（ｂの和）≧１を満足するものとする。）

B in need not be the same. n shows the integer of 0-19. However, a + (sum of b) ≧ 1 is satisfied. )

  The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and a + (sum of b) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different.

The number of silicon atoms forming the crosslinkable silicon group may be one or two or more, but in the case of silicon atoms linked by a siloxane bond or the like, there may be about 20 silicon atoms.
Formula (3):

（式中、Ｒ^１，Ｘ，ａは前記と同じ）で表わされる架橋性珪素基が、入手が容易である点から好ましい。

A crosslinkable silicon group represented by the formula (wherein R ¹ , X and a are the same as described above) is preferable from the viewpoint of easy availability.

Specific examples of R ¹ include an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and R ¹ ₃ SiO—. And triorganosiloxy group. Of these, a methyl group is preferred.

  It does not specifically limit as a hydrolysable group shown by said X, What is necessary is just a conventionally well-known hydrolysable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable, and an alkoxy group, an amide group, and an aminooxy group are more preferable. An alkoxy group is particularly preferred from the viewpoint of mild hydrolysis and easy handling. Among the alkoxy groups, those having a small number of carbon atoms have high reactivity, and the reactivity decreases as the number of carbon atoms increases in the order of methoxy group> ethoxy group> propoxy group. Although it can be selected according to the purpose and use, a methoxy group or an ethoxy group is usually used.

  In the case of the crosslinkable silicon group represented by the formula (3), a is preferably 2 or more in consideration of curability. Usually, when a is 3, the curing rate is higher than when a is 2.

Specific examples of the crosslinkable silicon group include trialkoxysilyl groups (—Si (OR) ₃ ) such as trimethoxysilyl group and triethoxysilyl group, dialkoxy such as methyldimethoxysilyl group and methyldiethoxysilyl group. And a silyl group (—SiR ¹ (OR) ₂ ). Here, R is an alkyl group, preferably an alkyl group having 10 or less carbon atoms, and more preferably a methyl group or an ethyl group. Among these, the methyldimethoxysilyl group has mild reactivity and is also used as a crosslinkable silicon group of polyoxyalkylene produced industrially. Recently, polyoxyalkylene polymers having a highly reactive trimethoxysilyl group bonded thereto have been known. Also in the present invention, a polyoxyalkylene polymer to which a trimethoxysilyl group is bonded can be used.

  One type of crosslinkable silicon group may be used, or two or more types may be used in combination. The crosslinkable silicon group can be present in the main chain, the side chain, or both. It is preferable that a crosslinkable silicon group is present at the end of the molecular chain in view of excellent cured product properties such as tensile properties of the cured product.

  At least one crosslinkable silicon group may be present in one molecule of the polymer, preferably 1.1 to 5. When the number of crosslinkable silicon groups contained in the molecule is less than one, the curability is insufficient, and when the number is too large, the network structure becomes too dense, and good mechanical properties are not exhibited.

  The polyoxyalkylene polymer used in the present invention is essentially a polymer having a repeating unit represented by the formula (4).

（式中、Ｒ^２は２価の有機基）

(Wherein R ² is a divalent organic group)

R ² in Formula (4) is preferably a linear or branched alkylene group having 1 to 14 carbon atoms, and more preferably 2 to 4 carbon atoms. Specific examples of the repeating unit represented by the formula (4) include the following repeating units.

  The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, it is preferably made of a polymer mainly composed of oxypropylene.

  The polyoxyalkylene polymer may be linear or branched. The number average molecular weight of the polyoxyalkylene polymer is preferably about 500 to 50,000, more preferably 5,000 to 40,000.

  As a method for synthesizing a polyoxyalkylene polymer, for example, a polymerization method using an alkali catalyst such as KOH, for example, JP-A Nos. 61-197631, 61-215622, 61-215623, and 61-215623 can be used. Polymerization method using an organoaluminum-porphyrin complex catalyst obtained by reacting an organoaluminum compound and a porphyrin as shown, for example, a double metal cyanide complex shown in JP-B-46-27250 and JP-B-59-15336 Examples of the polymerization method using a catalyst include, but are not limited to, a polymerization method. According to the polymerization method using an organic aluminum-porphyrin complex catalyst or the polymerization method using a double metal cyanide complex catalyst, the number average molecular weight is 6,000 or more, the Mw / Mn is 1.6 or less, the high molecular weight, and the molecular weight distribution is narrow. Coalescence can be obtained.

  The main chain skeleton of the polyoxyalkylene polymer may contain other components such as a urethane bond component. Examples of the urethane bond component include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate and polyoxyalkylenes having a hydroxyl group; What can be obtained from this reaction can be mentioned.

  The introduction of a crosslinkable silicon group into an oxyalkylene polymer is reactive to this functional group in an oxyalkylene polymer having a functional group such as an unsaturated group, hydroxyl group, epoxy group or isocyanate group in the molecule. Can be carried out by reacting a compound having a functional group and a crosslinkable silicon group (hereinafter, this reaction method is referred to as a polymer reaction method).

  As a specific example of the polymer reaction method, a hydrosilane or mercapto compound is produced by reacting an unsaturated group-containing oxyalkylene polymer with a hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group to form a crosslinkable silicon group. The method of obtaining the oxyalkylene type polymer which has can be mention | raise | lifted. An unsaturated group-containing oxyalkylene polymer is obtained by reacting a polyoxyalkylene polymer having a functional group such as a hydroxyl group with an organic compound having an active group and an unsaturated group reactive to the functional group. A polyoxyalkylene polymer containing a saturated group can be obtained.

  Other specific examples of the polymer reaction method include a method of reacting a polyoxyalkylene polymer having a hydroxyl group at a terminal with a compound having an isocyanate group and a crosslinkable silicon group, or an oxyalkylene polymer having an isocyanate group at a terminal. A method of reacting a compound with a compound having an active hydrogen group such as a hydroxyl group or an amino group and a crosslinkable silicon group can be given. When an isocyanate compound is used, an oxyalkylene polymer having a crosslinkable silicon group can be easily obtained. The polymer reaction method can be applied to polymers other than oxyalkylene polymers.

  Oxyalkylene polymers having a crosslinkable silicon group are disclosed in JP-B Nos. 45-36319 and 46-12154, JP-A Nos. 50-156599, 54-6096, 55-13767, and 57-164123. No. 3-2450, US Pat. No. 3,632,557, US Pat. No. 4,345,053, US Pat. No. 4,960,844, JP-A-2005-213446, JP-A-2005-306871, International Patent Publication WO2007 It is described in each publication such as -040143.

  In the present invention, a (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group can be used in combination with an oxyalkylene polymer having a crosslinkable silicon group ((meth) acrylic acid is an acrylic polymer). Acid or methacrylic acid). When such a polymer is used in combination, the cured sealing material has excellent adhesion to the substrate and weather resistance. The (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group is essentially a polymer having a repeating unit represented by the formula (5).

（式中、Ｒ^３は水素原子またはメチル基、Ｒ^４はアルキル基を示す）

(Wherein R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group)

R ⁴ in Formula (5) is an alkyl group, and an alkyl group having 1 to 30 carbon atoms is preferable. R ⁴ may be linear or branched. Moreover, the substituted alkyl group which has a halogen atom, a phenyl group, an epoxy group, an amino group, etc. may be sufficient. Examples of R ⁴ include methyl group, ethyl group, propyl group, n-butyl group, t-butyl group, 2-ethylhexyl group, lauryl group, tridecyl group, cetyl group, stearyl group, and behenyl group. it can.

The oxyalkylene polymer having a crosslinkable silicon group in the present invention, further (C) having a crosslinkable silicon group and (meth) acrylic acid alkyl ester-based polymer can be used in combination ((meth) acrylic Acid represents acrylic acid or methacrylic acid). When such a polymer is used in combination, the cured sealing material has excellent adhesion to the substrate and weather resistance. (C) The (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group is essentially a polymer having a repeating unit represented by the formula (5).

  Examples of monomer units other than formula (5) include acrylic acid such as acrylic acid and methacrylic acid; monomers containing amide groups such as acrylamide, methacrylamide, N-methylolacrylamide, and N-methylolmethacrylamide; Other examples include monomer units derived from acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, and the like.

  The (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group is used by mixing with an oxyalkylene polymer. In this case, a (meth) acrylic acid ester monomer having a crosslinkable silicon group and a molecular chain represented by formula (6) is highly compatible with an oxyalkylene polymer having a crosslinkable silicon group. The copolymer which consists of a body unit and the (meth) acrylic acid ester monomer unit represented by Formula (7) is preferable.

（式中、Ｒ^３は前記に同じ、Ｒ^５は炭素数１〜５のアルキル基を示す）で表される（メタ）アクリル酸エステル単量体単位と、下記式（７）：

(Wherein R ³ is the same as above, R ⁵ represents an alkyl group having 1 to ⁵ carbon atoms) and a (meth) acrylate monomer unit represented by the following formula (7):

（式中、Ｒ^３は前記に同じ、Ｒ^６は炭素数６以上のアルキル基を示す）

(Wherein R ³ is the same as above, and R ⁶ is an alkyl group having 6 or more carbon atoms)

As R < ⁵ > of Formula (6), C1-C5, such as a methyl group, an ethyl group, a propyl group, n-butyl group, t-butyl group, etc., Preferably it is 1-4, More preferably, it is 1-2. And an alkyl group. Incidentally, R ⁵ may be a kind, or may be a mixture of two or more.

R ^{6 in} formula (7) is, for example, a 2-ethylhexyl group, a lauryl group, a tridecyl group, a cetyl group, a stearyl group, a behenyl group or the like having 6 or more carbon atoms, usually 7-30, preferably 8-20 long. And an alkyl group of the chain. R ⁶ may be a single type or a mixture of two or more types. Moreover, the weight ratio of the monomer unit of the formula (6) and the monomer unit of the formula (7) is preferably 95: 5 to 40:60, and more preferably 90:10 to 60:40.

  The (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group may be linear or branched, and preferably has a number average molecular weight of about 500 to 50,000, preferably 1,000 to 30. Is more preferred.

  The (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group can usually be obtained by radical copolymerization of a (meth) acrylic acid alkyl ester and a (meth) acrylic acid alkyl ester having a crosslinkable silicon group. . Further, when an initiator having a crosslinkable silicon group or a chain transfer agent having a crosslinkable silicon group is used, the crosslinkable silicon group can be introduced into the molecular chain terminal.

  JP 2001-040037 A, JP 2003-048923 A and JP 2003-048924 A have a crosslinkable silicon group (meth) obtained by using a mercaptan having a crosslinkable silicon group and a metallocene compound. Acrylic acid alkyl ester polymers are described. Moreover, the synthesis example of Unexamined-Japanese-Patent No. 2005-026881 describes the (meth) acrylic-acid alkylester type polymer which has a crosslinkable silicon group by high temperature continuous polymerization.

  As disclosed in JP-A-2000-086999, a (meth) acrylic acid alkyl ester-based polymer having a crosslinkable silicon group, in which a crosslinkable silicon group is introduced at a high ratio at the molecular chain terminal, Are known. Since such a polymer is produced by living radical polymerization, a crosslinkable silicon group can be introduced into the molecular chain terminal at a high rate. In the present invention, a (meth) acrylic acid alkyl ester polymer as described above can be used.

  Specific examples of a mixture of a (meth) acrylic acid ester-based polymer having a crosslinkable silicon group and an oxyalkylene polymer having a crosslinkable silicon group are disclosed in JP-A-59-122541, JP-A-63-112642, and JP-A-6-126. -172631, and JP-A-10-251552. JP-A-59-78223, JP-A-59-168014, JP-A-60-228516, JP-A-60-228517, etc. disclose oxyalkylene polymers having a crosslinkable silicon group. (Meth) acrylic acid ester-based monomer is polymerized in the presence of a mixture of an oxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group. The method of obtaining is described.

(C) The (meth) acrylic acid ester-based polymer having a crosslinkable silicon group is 10 to 200 parts by weight, more preferably 20 to 20 parts by weight per 100 parts by weight of the (A) polyoxyalkylene polymer having a crosslinkable silicon group. It is preferable to use 100 parts by weight.

  Another organic polymer having a crosslinkable silicon group may be used in combination with the sealing material of the present invention. Examples of such polymers include polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or copolymers of butadiene and acrylonitrile and / or styrene, polybutadiene, and polyolefin-based polymers thereof. Hydrogenated polyolefin polymers such as hydrogenated polyolefin polymers obtained by hydrogenating polybasic acids such as adipic acid, terephthalic acid and succinic acid and polyhydric alcohols such as bisphenol A, ethylene glycol and neopentyl glycol; Polyester polymers such as condensation polymers of lactones and ring-opening polymers of lactones; nylon 6 by ring-opening polymerization of ε-caprolactam, nylon 6,6 by condensation polymerization of hexamethylenediamine and adipic acid, hexamethylenediamine and sebacine Nai by condensation polymerization of acid 6.10, Nylon 11 by condensation polymerization of ε-aminoundecanoic acid, Nylon 12 by ring-opening polymerization of ε-aminolaurolactam, Copolymer nylon having two or more components among the above nylons Examples thereof include a polysulfide polymer; a polycarbonate polymer produced by condensation polymerization from bisphenol A and carbonyl chloride, a diallyl phthalate polymer, and the like.

  When a polymer other than an oxyalkylene polymer having a crosslinkable silicon group or a (meth) acrylic acid ester polymer having a crosslinkable silicon group is used in combination, the oxyalkylene polymer having a crosslinkable silicon group or a crosslinkable property The total amount of the oxyalkylene polymer having a silicon group and the (meth) acrylic acid ester polymer having a crosslinkable silicon group is 50% by weight or more, more preferably 70% by weight of the total amount of the organic polymer having a crosslinkable silicon group. In particular, 80% by weight or more is preferable.

  In the present invention, as the component (B), a chelate compound comprising an alkylphenol resin and a metal oxide and / or a metal hydroxide is used. Examples of alkylphenol resins include o-cresol, m-cresol, p-cresol, ethylphenol, iso-propylphenol, xylenol, 3,5-xylenol, butylphenol, pt-butylphenol, nonylphenol and various formaldehyde And a resol-type precondensate obtained by reacting aldehyde with acetaldehyde in the presence of an alkali catalyst and modified products thereof. A phenol compound other than alkylphenol, such as phenol, may be used in combination with alkylphenol. As the alkylphenol resin, an alkylphenol formaldehyde resin is preferable. In particular, an alkylphenol resin having two or more methylol groups in the molecule can be suitably used.

  Examples of commercially available alkylphenol resins include Sumitomo Bakelite Co., Ltd. Sumitrite Resin PR-22193, Sumitrite Resin PR-50994, Sumitrite Resin PR-175, Sumitrite Resin PR-50530, Sumitrite. Resin PR-51466, Sumilite Resin PR-28633, Takuro Chemical Industry Co., Ltd. Tack Roll 201, Tack Roll 250-I, Tack Roll 250-II, Tack Roll 250-III, Gunei Chemical Industry Co., Ltd. PR-4507 And Tamanol 521 manufactured by Arakawa Chemical Industries, Ltd., CKM904 manufactured by Showa Denko KK, and Hitachi Chemical manufactured by Hitachi Chemical Co., Ltd. Also included are those containing various auxiliary agents such as thickeners, solvents and plasticizers added and blended during the production of alkylphenol formaldehyde resins.

Examples of the metal oxide and / or metal hydroxide that are one raw material of the chelate compound (B) include magnesium oxide (MgO), calcium oxide (CaO), zinc oxide (ZnO), and titanium oxide (TiO ₂ ). , Cadmium oxide (CdO), lead oxide (PbO), magnesium hydroxide (Mg (OH) ₂ ), calcium hydroxide (Ca (OH) ₂ ), and the like.

  Among chelate compounds obtained from alkylphenol resins and metal oxides and / or metal hydroxides, chelate compounds consisting of t-butylphenol resin and magnesium oxide are preferred.

The compounding amount of the chelate compound (B) is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the oxyalkylene polymer (A). If the blending amount exceeds 50 parts by weight, the sealing material becomes hard and the elongation decreases. The blending amount is more preferably 2 to 40 parts by weight, and particularly preferably 3 to 30 parts by weight. When the blending amount is less than 1 part by weight, there is a tendency that a sufficient paint adhesion improving effect cannot be obtained for the obtained cured product. In this invention, the compounding quantity of (B) component uses 1-10 weight part with respect to 100 weight part of oxyalkylene type polymers (A).

  As a method for synthesizing the chelate compound (B), a known method may be used. For example, after dissolving the alkylphenol resin in a suitable solvent, the metal oxide and / or metal hydroxide is added in a ratio of 3 to 20 parts by weight with respect to 100 parts by weight of the resin, and stirred for several hours. A chelate compound (B) is obtained.

The sealing material of the present invention may be used in combination with various additives such as a curing catalyst (D) (silanol condensation catalyst), a filler, a plasticizer, an adhesion-imparting agent, a diluent, and other tackifiers as necessary. Can do.

  Curing catalysts include tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, titanium tetraacetylacetonate, etc .; dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide Dioctyltin dilaurate, dioctyltin maleate, dioctyltin diacetate, dioctyltin dineodecanate (dioctyltin diversate), dioctyltin oxide, tetravalent tin compounds such as dibutyltin oxide and phthalate, tin octylate, naphthenate Organic tin compounds such as divalent tin compounds such as tin oxide, tin stearate, and tin neodecanoate (tin versatic acid); aluminum trisacetylacetonate, aluminum Organoaluminum compounds such as umtris ethyl acetoacetate and diisopropoxyaluminum ethyl acetoacetate; bismuth salts such as bismuth-tris (2-ethylhexoate), bismuth-tris (neodecanoate) and organic carboxylic acid or organic amine Reaction products, etc .; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; organic lead compounds such as lead octylate; organic iron compounds such as iron naphthenate; organic vanadium compounds; butylamine, octylamine, lauryl Amine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethyl Minopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8- Amine compounds such as diazabicyclo (5,4,0) undecene-7 (DBU) or salts thereof with carboxylic acid, etc .; low molecular weight polyamide resin obtained from excess polyamine and polybasic acid; excess polyamine and epoxy Examples of reaction products with compounds; acidic phosphate compounds and the like.

These curing catalysts may be used alone or in combination of two or more. Of these curing catalysts, organometallic compounds or a combined system of organometallic compounds and an amine compound are preferred from the viewpoint of curability. Furthermore, dibutyltin maleate, a reaction product of dibutyltin oxide and a phthalate ester, dibutyltin diacetylacetonate, and dioctyltin dineodecanate are preferred because of their high curing speed. Moreover, a dioctyl tin compound is preferable from the viewpoint of environmental problems. The (D) curing catalyst is preferably used in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the polyoxyalkylene polymer (A) having a crosslinkable silicon group.

  As fillers, reinforcing fillers such as fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, kaolin, titanium oxide In addition, a filler such as bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white, glass balloon, shirasu balloon, organic balloon, organic fiber and inorganic fiber can be used.

  When it is desired to obtain a cured product having high strength by using these fillers, fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid and carbon black, surface-treated fine calcium carbonate, calcined clay, clay, When a filler selected from active zinc white and the like is used in an amount of 1 to 200 parts by weight per 100 parts by weight of the polyoxyalkylene polymer having a crosslinkable silicon group, preferable results are obtained. In addition, when it is desired to obtain a cured product having low strength and large elongation, a filler selected mainly from titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like is used. If it is used in the range of 5 to 500 parts by weight per 100 parts by weight of the same polymer, preferable results can be obtained. These fillers may be used alone or in combination of two or more.

  Plasticizers include phthalates such as diisodecyl phthalate, diundecyl phthalate, diisoundecyl phthalate, dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate; aliphatics such as dioctyl adipate, isodecyl succinate, dibutyl sebacate, etc. Dibasic acid esters; Glycol esters such as diethylene glycol dibenzoate and pentaerythritol ester; Aliphatic esters such as butyl oleate and methyl acetyl ricinoleate; Epoxidized soybean oil, epoxidized linseed oil, epoxy benzyl stearate, etc. Epoxy plasticizers such as: polyester plasticizers such as polyesters of dibasic acids and dihydric alcohols; polyethers such as polypropylene glycol and derivatives thereof; ) Poly (meth) acrylate plasticizers such as alkyl acrylate esters; polystyrenes such as poly-α-methylstyrene and polystyrene; polybutadiene, butadiene-acrylonitrile copolymers, polychloroprene, polyisoprene, polyisobutene, paraffinic carbonization Plasticizers such as hydrogen, naphthenic hydrocarbons, paraffin-naphthene mixed hydrocarbons and chlorinated paraffins can be used alone or in the form of a mixture of two or more.

  In particular, polyether plasticizers such as polypropylene glycol and its derivatives, poly (meth) acrylate plasticizers, polyisobutene, paraffin and the like that do not contain an unsaturated bond in the polymer main chain are preferred from the viewpoint of weather resistance. In particular, polyether plasticizers such as polypropylene glycol and derivatives thereof, and poly (meth) acrylate plasticizers, which are polymer plasticizers, are preferable. When using a plasticizer, it is preferable to add 1-200 weight part with respect to 100 weight part of polyoxyalkylene type polymer which has a crosslinkable silicon group, Furthermore, 5-150 weight part is added.

  Examples of the adhesion-imparting agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- Amino group-containing silanes such as (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, 1,3-diaminoisopropyltrimethoxysilane; Epoxy group-containing silanes such as glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Γ-mercaptopropyltrimethoxysilane, Mercapto group-containing silanes such as γ-mercaptopropylmethyldimethoxysilane; vinyl-type unsaturated groups such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-acryloyloxypropylmethyldimethoxysilane Silanes; Chlorine atom-containing silanes such as γ-chloropropyltrimethoxysilane; Isocyanate-containing silanes such as γ-isocyanatopropyltriethoxysilane and γ-isocyanatopropylmethyldimethoxysilane; methyldimethoxysilane, trimethoxysilane, methyldi Specific examples include hydrosilanes such as ethoxysilane, but are not limited thereto.

  If the adhesiveness-imparting agent is added too much, the modulus of the cured product is increased, and if it is too small, the adhesiveness is lowered. It is preferable to add 1 to 15 parts by weight, and it is more preferable to add 0.5 to 10 parts by weight.

  You may mix | blend a solvent and a diluent for the improvement of workability | operativity, the fall of a viscosity, etc. Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate and cellosolve; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Examples of the diluent include normal paraffin and isoparaffin.

  A tackifier other than the component (B) may be added in order to improve the wettability to the adherend and increase the peel strength. Examples include petroleum resin-based, rosin / rosin ester-based, acrylic resin-based, terpene resin, hydrogenated terpene resin, phenolic resin copolymer thereof, and phenolic resin-based tackifier resins.

  Examples of other additives include sagging inhibitors such as hydrogenated castor oil, organic bentonite, and calcium stearate, colorants, antioxidants, ultraviolet absorbers, and light stabilizers. Furthermore, additives such as other resins such as epoxy resins, curing agents such as epoxy resin curing agents, physical property modifiers, storage stability improvers (dehydrating agents), lubricants and foaming agents should be added as necessary. Is possible.

  The sealing material of the present invention can be used as a one-pack type sealing material having all components as a mixture, or as a two-pack type sealing material having a resin component having a crosslinkable silicon group and a curing catalyst component as separate components. Although it is possible, it is desirable to use it as a one-pack type sealing material.

  Examples of paints that can be used on the surface of the sealing material of the present invention include thermoplastic (meth) acrylic paints, thermosetting (meth) acrylic paints, polyurethane paints, acrylic urethane paints, and silicone-modified urethanes. Paints, melamine paints, epoxy paints, acrylic modified alkyd paints, amine alkyd paints, alkyd melamine paints, polyether melamine paints, polyester melamine paints, and the like. The paint may be a water-based paint or a solvent-based paint.

  Examples of coating methods include spray coating by spraying, brush coating, and roller coating, and any method can be employed.

(Synthesis Example 1) Synthesis of metal chelate compound of alkylphenol resin 100 parts by weight of Tamanol 521 (manufactured by Arakawa Chemical Industries, Ltd.) as an alkylphenol resin was dissolved in 100 parts by weight of toluene, and then magnesium oxide (MgO) was used as a metal oxide. 10 parts by weight was added and stirred at 30 ° C. for 10 hours to obtain a chelate compound (B1) of an alkylphenol resin and magnesium oxide.

(Synthesis Example 2)
A chelate compound (B2) of an alkylphenol resin and magnesium oxide was obtained in the same manner as in Synthesis Example 1 except that 100 parts by weight of CKM904 (manufactured by Showa Denko KK) was used as the alkylphenol resin.

  The evaluation methods of the paint adhesion and water-resistant adhesion of the sealing material in the examples are as follows.

(Paint adhesion)
A sealant was applied to a thickness of 3 mm, cured under curing conditions for 7 days under conditions of 23 ° C. and 50% relative humidity (RH), and then a paint was applied to the surface of the cured product with a brush. Cured for 7 days under the condition of% RH to obtain a test specimen. The paint used is as shown in Table 1. A cross cut test (25 pieces) at intervals of 2 mm was performed on this test body using cellophane tape made by Nichiban Co., Ltd. The coating adhesion was determined by the percentage (%) of the number of grids remaining on the cured product surface with respect to the total number of grids. The criteria for judging paint adhesion were as follows.
A: 80% or more B: 40% or more and less than 80% X: less than 40%.

(Water resistant adhesiveness)
The test was carried out in accordance with “4.21 Tensile Adhesion Test” in JIS A1439: 1997 “Testing Method of Sealant for Building” (test temperature: 23 ° C.). The test body was prepared by curing a test body in which a sealing material was placed on a ceramic siding material as an adherend for 14 days at 23 ° C. and 50% relative humidity. The fracture condition was evaluated as follows and indicated as initial adhesiveness. Moreover, after immersing the test piece produced by curing at 23 ° C. and 50% relative humidity for 14 days in 50 ° C. water for 7 days, a tensile test was performed to evaluate the fracture state. The criteria for determining adhesiveness were as follows.
◎: Cohesive failure ○: When thin layer cohesive failure is confirmed ×: When interface fracture is confirmed

(Physical properties of sealing materials)
The test was carried out in accordance with “4.21 Tensile Adhesion Test” in JIS A1439: 1997 “Testing Method of Sealant for Building” (test temperature: 23 ° C.). The test body was prepared by curing a test body in which a sealing material was cast on a siding material as an adherend for 14 days at 23 ° C. and 50% relative humidity. Tensile tests were conducted to evaluate the elongation at break, and the physical properties of the sealing material were shown. The criteria for determining the physical properties of the sealing material were as follows.
◎: 400% or more ○: 100% or more and less than 400% ×: less than 100%

Example 1
As shown in Table 1, (A) Kaneka MS polymer S203H (manufactured by Kaneka Corporation), (B) alkylphenol resin, metal oxide and / or metal as a polyoxyalkylene polymer having a crosslinkable silicon group As a chelate compound comprising a hydroxide, a magnesium chelate compound of the alkylphenol resin obtained in Synthesis Example 1, an ultraviolet absorber, a plasticizer, a dehydrating agent, and a filler are respectively charged in predetermined amounts, and heated and mixed under stirring. The compounded material was dehydrated. In addition, the quantity of (B) component in Table 1 is the weight of solid content which does not contain a solvent. Further, a predetermined amount of an adhesion-imparting agent and a curing catalyst were added and mixed by stirring to prepare a moisture curable sealing material. The moisture curable sealant was evaluated for paint adhesion, water-resistant adhesion and sealant physical properties. The results are shown in Table 1.

* 1: Crosslinkable silicon group-containing polyoxyalkylene polymer (trade name; S203H, manufactured by Kaneka Corporation)
* 2: Crosslinkable silicon group-containing acrylic modified polyoxyalkylene polymer (trade name; S943, manufactured by Kaneka Corporation)
* 3: Magnesium chelate compound of alkylphenol resin obtained in Synthesis Example 1 * 4: Magnesium chelate compound of alkylphenol resin obtained in Synthesis Example 2 * 5: Alkylphenol resin used as a raw material in Synthesis Example 1 (trade name; Tamanol) 521, manufactured by Arakawa Chemical Industries, Ltd.)
* 6: Alkylphenol resin used as raw material in Synthesis Example 2 (trade name: CKM904, manufactured by Showa Denko KK)
* 7: Terpene phenol resin (trade name: YS Polystar T100, manufactured by Yasuhara Chemical Co., Ltd.)
* 8: Styrene resin (trade name: FTR7100, manufactured by Mitsui Chemicals, Inc.)
* 9: Benzotriazole-based UV absorber (trade name; ADK STAB LA36, manufactured by Asahi Denka Co., Ltd.)
* 10: Polypropylene glycol (trade name; PML3012, manufactured by Asahi Glass Co., Ltd.)
* 11: Vinyltrimethoxysilane (trade name: KBM1003, manufactured by Shin-Etsu Chemical Co., Ltd.)
* 12: Heavy calcium carbonate (trade name: Whiten SB, manufactured by Shiroishi Kogyo Co., Ltd.)
* 13: Surface treated calcium carbonate (trade name: Calfine 500, manufactured by Maruo Calcium Co., Ltd.)
* 14: Silane coupling material (trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.)
* 15: Tetravalent tin compound (trade name: U-220, manufactured by Nitto Kasei Co., Ltd.)
* 16: Water-based paint 1 (trade name: Jolipat JP100, manufactured by Aika Industry Co., Ltd.)
* 17: Water-based paint 2 (trade name: Super E, manufactured by Kikusui Chemical Co., Ltd.)
* 18: Solvent-based paint 1 (Product name: EX Sealer, manufactured by SK Kaken Co., Ltd. * 19: Weak solvent-based paint (Product name: Clean Mild Urethane, manufactured by SK Kaken Co., Ltd.)

(Example 2)
A moisture-curable sealing material was prepared in the same manner as in Example 1 except that 10 parts by weight of the chelating compound (B) was used. This moisture curable sealant was evaluated for paint adhesion and water-resistant adhesion. The results are shown in Table 1.

( Reference Example 1 )
A moisture-curable sealing material was prepared in the same manner as in Example 1 except that 30 parts by weight of the chelating compound (B) was used. This moisture curable sealant was evaluated for paint adhesion and the like. The results are shown in Table 1.

(Example 3 )
(A) Kaneka MS polymer S943 (manufactured by Kaneka Corporation), which is a crosslinkable silicon group-containing acrylic-modified polyoxyalkylene polymer, replaces Kaneka MS polymer S203H as a polyoxyalkylene polymer having a crosslinkable silicon group. A moisture curable sealant was prepared in the same manner as in Example 1 except that was used. This moisture curable sealant was evaluated for paint adhesion and the like. The results are shown in Table 1.

(Example 4 )
A moisture-curable sealing material was prepared in the same manner as in Example 1 except that the magnesium chelate compound of the alkylphenol resin obtained in Synthesis Example 2 was used as the chelate compound of component (B). This moisture curable sealant was evaluated for paint adhesion and the like. The results are shown in Table 1.

(Comparative Example 1)
(B) A moisture curable sealing material was used in the same manner as in Example 1 except that the alkylphenol resin (Tamanol 521, manufactured by Arakawa Chemical Industries, Ltd.) used as a raw material in Synthesis Example 1 was used instead of the chelate compound of Component (B). Prepared. This moisture curable sealant was evaluated for paint adhesion and water-resistant adhesion. The results are shown in Table 1.

(Comparative Example 2)
A moisture curable sealing material was prepared in the same manner as in Example 1 except that the alkylphenol resin (CKM904, manufactured by Showa Denko KK) used as a raw material in Synthesis Example 2 was used instead of the chelate compound of component (B). . This moisture curable sealant was evaluated for paint adhesion and water-resistant adhesion. The results are shown in Table 1.

(Comparative Example 3)
A moisture curable sealant was prepared in the same manner as in Example 1 except that a terpene phenol resin (YS Polystar T100, manufactured by Yasuhara Chemical Co., Ltd.) was used instead of the chelate compound of component (B). This moisture curable sealant was evaluated for paint adhesion and water-resistant adhesion. The results are shown in Table 1.

(Comparative Example 4)
A moisture curable sealant was prepared in the same manner as in Example 1 except that a styrene resin (FTR 7100, manufactured by Mitsui Chemicals, Inc.) was used instead of the chelate compound of component (B). This moisture curable sealant was evaluated for paint adhesion and water-resistant adhesion. The results are shown in Table 1.

(Comparative Example 5)
A moisture-curable sealing material was prepared in the same manner as in Example 1 except that 0.5 part by weight of the chelating compound (B) was used. This moisture curable sealant was evaluated for paint adhesion and water-resistant adhesion. The results are shown in Table 1.

(Comparative Example 6)
A moisture-curable sealing material was prepared in the same manner as in Example 1 except that 60 parts by weight of the chelating compound (B) was used. This moisture curable sealant was evaluated for paint adhesion and water-resistant adhesion. The results are shown in Table 1.

Claims (10)

(A) 100 parts by weight of a polyoxyalkylene polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having a crosslinkable silicon group that can be crosslinked by forming a siloxane bond with moisture, (B) A moisture-curable sealant containing 1 to 10 parts by weight of a chelate compound comprising an alkylphenol resin and a metal oxide and / or metal hydroxide. The crosslinkable silicon group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond with moisture is a crosslinkable silicon group represented by the formula (1). The moisture-curable sealing material according to claim 1.

(In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or R ¹³ SiO— ( R ¹ is the same as above, and when two or more R ¹ are present, they may be the same or different, and X is a hydroxyl group or a hydrolyzable group. And when two or more X are present, they may be the same or different, a represents 0, 1, 2 or 3, and b represents 0, 1 or 2. Also, n formulas (2):

B in need not be the same. n shows the integer of 0-19. However, a + (sum of b) ≧ 1 is satisfied. ) The moisture-curable sealing material according to claim 2, wherein the crosslinkable silicon group represented by the formula (1) is a crosslinkable silicon group represented by the formula (3).

(Wherein R ¹ , X and a are the same as above)   The moisture-curable sealing material according to any one of claims 1 to 3, wherein the hydrolyzable group is an alkoxy group in the crosslinkable silicon group.   The moisture-curable sealing material according to claim 4, wherein the hydrolyzable group is a methoxy group.   The moisture curable sealant according to any one of claims 1 to 5, wherein the polyoxyalkylene polymer is a polyoxypropylene polymer. Further, (C) a (meth) acrylic acid ester-based polymer having a hydroxyl group or hydrolyzable group bonded to a silicon atom and having a crosslinkable silicon group that can be crosslinked by forming a siloxane bond with moisture (A) ) 20 to 100 with respect to 100 parts by weight of a polyoxyalkylene polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having a crosslinkable silicon group that can be crosslinked by forming a siloxane bond with moisture. The moisture-curable sealing material according to any one of claims 1 to 6, comprising a part by weight.   (B) A chelate compound consists of a t-butylphenol resin and magnesium oxide, The moisture hardening sealing material of any one of Claims 1-7 characterized by the above-mentioned. Furthermore, (D) the curing catalyst (A) a polyoxyalkylene polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having a crosslinkable silicon group that can be crosslinked by forming a siloxane bond with moisture. The moisture-curable sealing material according to any one of claims 1 to 8, comprising 0.5 to 10 parts by weight with respect to 100 parts by weight.   The moisture curable sealant according to any one of claims 1 to 9, wherein the sealant is a building sealant.