JP4548072B2 - Two-component curable polyurethane resin composition - Google Patents

Description

  The present invention relates to a two-component curable polyurethane resin composition.

  A polyisocyanate compound having two or more isocyanate groups (—NCO) in the molecule, such as a urethane prepolymer, forms a three-dimensional crosslinked structure by reaction with a curing agent such as an amine compound or a polyol compound, and the strength, elongation, It becomes a polyurethane cured product excellent in wear resistance, oil resistance and the like. Conventionally, a polyurethane resin composition containing a polyisocyanate compound as a main component has been widely used as a joint material, a sealant, an adhesive, and the like.

When a curing agent such as an amine compound or a polyol compound and a polyisocyanate compound are stored in a mixed state, there is a problem that gelation occurs during storage or the curing reaction proceeds, resulting in poor storage stability. Further, if the compatibility between the polyisocyanate compound and the curing agent is poor, there is a problem that they are separated during storage and become an inhomogeneous cured product. Furthermore, since the one-component polyurethane resin composition is cured by moisture, there is a problem that it cannot be applied to a site that requires deep curing.
In order to avoid these problems, the polyurethane resin composition is usually used as a so-called two-component system (two-component type) that is mixed during work.

  As a two-component polyurethane resin composition, for example, Patent Document 1 discloses a method for producing a structural polyurethane adhesive “structural adhesion comprising mixing and reacting a mixture of a first component and a second component. A first component comprising a hydrogenated polybutadiene polyol having a functionality of 1.5 to 2.5, and a second component comprising a polyisocyanate having a functionality of 2 to 3. Or a functionality of 1.5 to 2.5, selected from the group consisting of polyester polyols, polyether polyols, and hydroxy-terminated copolymers of dialkylsiloxanes and alkylene oxides, and 500 Comprising a polymer polyol having a number average molecular weight of 10000 to 10000, the second component having a functionality of 1.5 to 2.5 and 3 Comprising an isocyanate-terminated prepolymer obtained by reacting a hydrogenated polybutadiene polyol having a 1,2 vinyl content before hydrogenation of ˜70% by weight with an excess of a polyisocyanate having a functionality of 2-3. , A process wherein the first component and the second component are present in such an amount that the NCO: OH molar ratio is greater than 1.05 and not greater than 1.6.

  Patent Document 2 discloses a two-component polyurethane adhesive that can be particularly suitably used for laminating and bonding a polyester film and a fluororesin film, which has been difficult to bond with each other, and has excellent bonding performance and bonding durability. An agent composition is described. Specifically, a main component comprising a terminal isocyanate group-containing urethane prepolymer from a polymer polyol (a1) having a number average molecular weight of 800 to 3,500 and an excess of aliphatic and / or alicyclic polyisocyanate (a2). (A), a curing agent (B) comprising a polydiene polyol (b1) having a number average molecular weight of 1,000 to 3,500 and / or a terminal hydroxyl group-containing derivative (b2) thereof, and an organic solvent (C) A two-component polyurethane adhesive composition is described.

Special table 2001-514277 gazette JP 2000-290630 A

However, the structural polyurethane adhesive produced by the production method described in Patent Document 1 can adhere sheets and films such as vinyl chloride (vinyl chloride), but is solid at room temperature and is used when used. Workability was poor because heating was required. In addition, according to the production method of Patent Document 1, “the first component and the second component are present in such an amount that the NCO: OH molar ratio is larger than 1.05 and not larger than 1.6”. Contains an excess of isocyanate groups. Therefore, when cured in an environment where a large amount of moisture exists (for example, outdoors during rain, rippling, underwater, etc.), there is a problem of foaming because the isocyanate groups react with water to generate carbon dioxide.
In addition, the two-component polyurethane adhesive composition described in Patent Document 2 may cause problems when used in an environment such as outdoors where a large amount of water is present. Moreover, since the organic solvent is used in order to improve workability | operativity, the load to an environment is large. Therefore, a two-component curable polyurethane resin composition that can be used without a solvent is required from the viewpoint of VOC reduction, which has been a problem in recent years.

  By the way, among the polyols used as raw materials or curing agents for urethane prepolymers, polybutadiene polyol has low polarity and excellent hydrophobicity. On the other hand, polyether polyol has a property of being excellent in adhesiveness with vinyl chloride or the like because of its high polarity. However, these polyols have low compatibility due to the difference in polarity, causing problems such as causing layer separation when used in combination.

  Accordingly, an object of the present invention is to provide a two-component curable polyurethane resin composition that is excellent in adhesiveness with vinyl chloride, workability, and adhesiveness in water (adhesiveness in water) and suppresses foaming during curing. And

As a result of intensive studies, the inventor contains a main agent containing a specific urethane prepolymer (A) and an isocyanurate group-containing polyisocyanate (B), and a polyol (C) containing a polybutadiene polyol at a specific ratio. When the molar ratio (NCO / OH) of the isocyanate group contained in the main agent to the hydroxy group contained in the curing agent is within a specific range, the adhesiveness with vinyl chloride, workability, and water The present invention was completed by finding out that it has excellent adhesiveness and can suppress foaming during curing.
That is, the present invention provides the following (1) to (5).

(1) Contains a urethane prepolymer (A) obtained by reacting a polyol (a) containing 10 to 60% by mass of a polybutadiene polyol, a polyisocyanate (b), and an isocyanurate group-containing polyisocyanate (B). With the main agent,
A curing agent containing a polyol (C) containing 10-50 mass% of polybutadiene polyol,
A two-component curable polyurethane resin composition having a molar ratio (NCO / OH) of an isocyanate group contained in the main agent to a hydroxy group contained in the curing agent of 0.8 to 1.05.

  (2) The two-component curable polyurethane resin composition according to (1), wherein the polyol (a) and / or the polyol (C) includes a polyether polyol.

  (3) The two-component curable polyurethane resin composition according to the above (1) or (2), wherein the polyol (a) and / or the polyol (C) contains a castor oil-based polyol.

  (4) Any of the above (1) to (3), wherein the molar ratio (NCO / OH) of the isocyanate group of the polyisocyanate (b) to the hydroxy group of the polyol (a) is 1.7 to 2.0. The two-component curable polyurethane resin composition according to claim 1.

  (5) The two-component curable polyurethane resin composition according to any one of (1) to (4), wherein the main agent and / or the curing agent contains a plasticizer.

  The two-component curable polyurethane resin composition of the present invention is excellent in adhesion to vinyl chloride, particularly soft vinyl chloride, workability, and underwater adhesion, and can suppress foaming during curing.

Hereinafter, the present invention will be described in more detail.
The two-component curable polyurethane resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) reacts a polyol (a) containing 10 to 60% by mass of a polybutadiene polyol with a polyisocyanate (b). The urethane prepolymer (A) to be formed, a main agent containing the isocyanurate group-containing polyisocyanate (B), and a curing agent containing a polyol (C) containing 10 to 50% by mass of a polybutadiene polyol, and The molar ratio (NCO / OH) between the isocyanate group contained in the main agent and the hydroxy group contained in the curing agent is 0.8 to 1.05.

By the way, when a polyurethane resin composition using a polyol having a relatively high polarity main chain skeleton such as polyether polyol as a raw material is cured in water, water is easily adsorbed due to its high polarity, and water is entrained in the cured product. Therefore, there is a problem that foaming occurs.
On the other hand, since the polybutadiene polyol used in the composition of the present invention has a polybutadiene skeleton having a relatively low polarity, it is difficult to adsorb water. Therefore, the urethane prepolymer (A) having a polybutadiene skeleton and the composition of the present invention containing the polybutadiene polyol used as a curing agent are foamed without involving water in the cured product even when cured in water. Can be suppressed.

  From the point which is excellent by the characteristic mentioned above, in the composition of this invention, the sum total of the polybutadiene polyol contained in the said polyol (a) and the said polyol (C) is 25-75 mass% with respect to the total resin amount of a composition. It is preferable that it is 30 to 60% by mass. The total resin amount of the composition means the total mass of the urethane prepolymer (A), the isocyanurate group-containing polyisocyanate (B) and the polyol (C), and does not include plasticizers and other additives. And

Conventionally, since polybutadiene polyol and polyether polyol have low compatibility, when they are used in combination, problems such as layer separation may occur.
On the other hand, in the composition of the present invention, when a polyol (a) containing a low-polarity polybutadiene polyol is reacted with a polyisocyanate (b) to form a urethane prepolymer (A), a urethane bond is generated in the skeleton and the polarity becomes high. . Therefore, compatibility with the polyether polyol is improved, and problems such as layer separation can be suppressed. Moreover, since the obtained urethane prepolymer (A) has a polybutadiene skeleton, it is excellent in compatibility with the polybutadiene polyol contained in the curing agent.

Therefore, the polyol (a) as a raw material for the urethane prepolymer (A) can exhibit the excellent effects of the polybutadiene polyol as described above, and is excellent in the balance between workability and physical properties of the cured product. From 10 to 60% by mass of polybutadiene polyol. In view of these characteristics, the polyol (a) preferably contains 10 to 50% by mass of polybutadiene polyol, more preferably 20 to 40% by mass.
Moreover, in order to exhibit the outstanding effect which polybutadiene polyol as mentioned above has, and to balance workability | operativity and the physical property of hardened | cured material, the polyol (C) contained in a hardening | curing agent is polybutadiene polyol. Contains 50% by mass.

<Urethane prepolymer (A)>
The urethane prepolymer (A) is contained as a resin component in the main component of the composition of the present invention and is liquid at normal temperature. This urethane prepolymer (A) is obtained by reacting a polyol (a) containing 10 to 60% by mass of a polybutadiene polyol with a polyisocyanate (b).

The polybutadiene polyol is not particularly limited as long as it is a butadiene having a hydroxy group at its terminal and a copolymer thereof. For example, the structure of the polybutadiene polyol may include a trans type, a cis type, or a 1,2 vinyl type (1,2-addition type). Such a microstructure can generally be confirmed by ¹³ C nuclear magnetic resonance (NMR) spectra in chloroform.

  The number average molecular weight of the polybutadiene polyol is not particularly limited as long as it is liquid, but is preferably 1000 to 4000, for example. Within this range, there is an effect of excellent balance of physical properties of the cured product. It is more preferable that the number average molecular weight is 1000 to 2000 in that the effect is superior.

  The polybutadiene polyol may be produced according to a conventional method, or a commercially available product may be used.

A polybutadiene polyol may be used independently and may use 2 or more types together.
The amount of the polybutadiene polyol contained in the polyol (a) is as described above.

  The polyol (a) preferably contains a polyether polyol in addition to the polybutadiene polyol. When the polyether polyol is included, the skeleton of the polyether polyol has a relatively high polarity, so that the resulting composition has excellent adhesion to vinyl chloride (hereinafter also referred to as “vinyl chloride adhesion” for convenience). In addition, since polyether polyol has a relatively low viscosity, it is excellent in workability, is excellent in the balance of physical properties of the cured product, and is inexpensive.

The polyether polyol is not particularly limited, but preferably has 2 to 4 hydroxy groups and a number average molecular weight per hydroxy group of 100 to 5,000.
Examples of the polyether polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 4,4′-dihydroxyphenylpropane, and 4,4′-dihydroxy. At least one of polyhydric alcohols such as phenylmethane, glycerin, 1,1,1-trimethylolpropane, 1,2,5-hexanetriol, pentaerythritol, propylene oxide, ethylene oxide, butylene oxide, styrene oxide, etc. Examples include polyether polyols obtained by adding at least one kind.
Specific examples include polypropylene ether diol, polyethylene ether diol, polypropylene ether triol, polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran, and the like.
These polyether polyols may be used alone or in combination of two or more.

  The number average molecular weight of the polyether polyol is preferably 5,000 to 10,000, and more preferably 2,000 to 8,000.

  The polyether polyol may be produced according to a conventional method, or a commercially available product may be used.

  10-90 mass% of the said polyol (a) is preferable, and, as for content of polyether polyol, 40-70 mass% is more preferable.

  In a preferred embodiment, the polyol (a) contains a castor oil-based polyol in addition to the above-mentioned polyol. When a castor oil-based polyol is included, the viscosity is lowered and the workability is excellent. Further, since the castor oil-based polyol also acts as a compatibilizing agent for the polybutadiene polyol and the polyether polyol, the compatibility is further improved, layer separation can be suppressed, and the physical properties of the cured product are further improved.

  Examples of the castor oil-based polyol include castor oil, its alkylene oxide adduct, its epoxy compound, its halide, and derivatives such as transesterification products of divalent or higher polyhydric alcohols using castor oil as raw materials.

  The castor oil-based polyol may be produced according to a conventional method, or a commercially available product may be used.

  20-80 mass% of the said polyol (a) is preferable, and, as for content of a castor oil-type polyol, 30-50 mass% is more preferable.

  Examples of polyols other than the polyols described above include polyolefin polyols such as polyisoprene polyols; adipate polyols; lactone polyols; low molecular polyhydric alcohols and / or aromatic diols, and polybasic carboxylic acids. Condensates (condensation polyester polyols); lactone polyols; polycarbonate polyols, acrylic polyols, and the like can be used.

The polyisocyanate (b) is not particularly limited as long as it is a compound having two or more NCO groups in the molecule. Specific examples thereof include 2,4-tolylene diisocyanate (2,4-TDI), 2, 6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene Aromatic polyisocyanates such as diisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI); hexamethylene diisocyanate (HDI), trimethylhexamethylene Diisocyanate (TMHDI), lysine diisocyanate, aliphatic polyisocyanates such as norbornane diisocyanate methyl (NBDI); trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H ₆ XDI (hydrogenated XDI), _{H 12} MDI ( And alicyclic polyisocyanates such as hydrogenated MDI) and H ₆ TDI (hydrogenated TDI); carbodiimide-modified polyisocyanates of these polyisocyanate compounds; isocyanurate-modified polyisocyanates of these polyisocyanate compounds.
These may be used alone or in combination of two or more.
A monoisocyanate compound having only one NCO group in the molecule can also be used by mixing with a diisocyanate compound or the like.

  Among these, MDI and TDI are preferable because they are excellent in physical properties (particularly strength) of the cured product, and are inexpensive and easily available.

  The urethane prepolymer (A) is obtained by reacting the polyol (a) and the polyisocyanate (b). At this time, the molar ratio (NCO / OH) of the isocyanate group of the polyisocyanate (b) to the hydroxyl group of the polyol (a) is preferably 1.7 to 2.0, and is preferably 1.85 to 1.95. Is more preferable. If it is this range, the physical property of hardened | cured material will become favorable, without the viscosity of a urethane prepolymer (A) increasing.

  The manufacturing method of the said urethane prepolymer (A) can select the same method as a normal urethane prepolymer. Specifically, it can be obtained, for example, by heating and stirring a mixture of the above polybutadiene polyol, polyether polyol and castor oil-based polyol, and polyisocyanate at 50 to 100 ° C. Moreover, you may use urethanation catalysts, such as an organic tin compound, organic bismuth, and an amine, as needed.

  The said urethane prepolymer (A) may be used independently and may use 2 or more types together.

<Isocyanurate group-containing polyisocyanate (B)>
The isocyanurate group-containing polyisocyanate (B) contained in the main agent is not particularly limited as long as it is a liquid at room temperature and has at least one isocyanurate group (ring) and two or more isocyanate groups. Since the isocyanurate group-containing polyisocyanate (B) has a highly polar isocyanurate group, a composition having excellent adhesion to vinyl chloride, particularly soft vinyl chloride, can be obtained.

  The isocyanurate group-containing polyisocyanate (B) can be produced by known conditions and methods. For example, the isocyanate compound exemplified in the above polyisocyanate (b) and a catalyst are mixed, and usually at 50 to 150 ° C. It can be obtained by reaction.

Although it does not specifically limit as an isocyanate compound used for isocyanurate group containing polyisocyanate (B), HDI is preferable from the point which is a liquid at normal temperature and does not require a solvent.
The said isocyanate compound may be used independently and may use 2 or more types together.

  Specific examples of the catalyst include alkoxides such as sodium methylate, amine compounds such as triethylamine, carboxylates such as calcium naphthenate, and organometallic compounds such as dibutyltin dilaurate. These may be used alone or in combination of two or more.

  It is preferable that content of the said isocyanurate group containing polyisocyanate (B) is 1-5 mass% with respect to the said urethane prepolymer (A). When the content is within this range, the adhesiveness to polyvinyl chloride is excellent, and the elongation of the cured product can be sufficiently obtained.

<Polyol (C)>
The polyol (C) contained in the curing agent is liquid at normal temperature and contains 10-50% by mass of polybutadiene polyol. As the polyol (C), those basically the same as the polyol (a) can be used except that the content of the polybutadiene polyol is different. Therefore, since the polyol (C) contains a polybutadiene polyol in the same manner as the polyol (a), even when the composition of the present invention is cured in water, it suppresses foaming without involving water in the cured product. be able to. Moreover, when the said polyol (C) contains a polybutadiene polyol in said ratio, since it can suppress foaming in water and can prevent that a viscosity becomes high too much, the composition excellent in workability | operativity is obtained. can get. The polyol (C) preferably contains 20 to 40% by mass of a polybutadiene polyol from the viewpoint that a composition excellent in these characteristics can be obtained.

  The polyol (C) preferably contains a polyether polyol in addition to the polybutadiene polyol. This polyether polyol is the same as that contained in the polyol (a).

  10-90 mass% of the said polyol (C) is preferable, and, as for content of polyether polyol, 40-80 mass% is more preferable.

  In one preferred embodiment, the polyol (C) contains a castor oil-based polyol in addition to the polyol. This castor oil-based polyol is the same as that contained in the polyol (a).

  20-80 mass% of the said polyol (C) is preferable, and, as for content of a castor oil-type polyol, 30-50 mass% is more preferable.

  Examples of polyols other than the polyols described above include polyolefin polyols such as polyisoprene polyols; adipate polyols; lactone polyols; low molecular polyhydric alcohols and / or aromatic diols, and polybasic carboxylic acids. Condensates (condensation polyester polyols); lactone polyols; polycarbonate polyols, acrylic polyols, and the like can be used.

  In the composition of the present invention, the molar ratio (NCO / OH) of the sum of isocyanate groups contained in the main agent and the sum of hydroxy groups contained in the curing agent is 0.8 to 1.05. When the molar ratio is within this range, even after mixing the main agent and the curing agent, it is liquid for a certain period of time and has fluidity, so that it can be injected into various construction sites. Moreover, since the process of heating and melting at the time of use like the structural polyurethane adhesive described in Patent Document 1 is unnecessary, the workability is excellent. In view of these characteristics, the molar ratio is preferably 0.9 to 1.05, more preferably 0.95 to 1.05.

In one preferred embodiment, the composition of the present invention further contains a plasticizer. The plasticizer is contained in one or both of the main agent and the curing agent. When a plasticizer is used, since the viscosity is low, a composition excellent in workability can be obtained. Further, the compatibility between the polybutadiene polyol and the polyether polyol and the compatibility between the main agent and the curing agent are further improved, so that a uniform composition can be obtained, and the physical properties of the cured product are further improved.
When a plasticizer is contained in the main agent, it is preferably mixed with the polyol (a) and the polyisocyanate (b) during the production of the urethane prepolymer (A). This is because the urethane prepolymer (A) having excellent physical properties can be obtained by improving the compatibility between the polybutadiene polyol and the polyether polyol contained in the polyol (a). When the urethane prepolymer (A) is produced in this manner, a liquid mixture in which the plasticizer is dispersed in the urethane prepolymer (A) (resin component) is obtained.
Here, in this specification, the term "urethane prepolymer (A)" is used in the meaning which does not include the plasticizer.

Specific examples of the plasticizer include dioctyl phthalate (DOP), dibutyl phthalate (DBP), diethyl phthalate (DEP), dimethyl phthalate (DMP), diisononyl phthalate (DINP), dinonyl phthalate (DNP), Phthalates such as butylbenzyl phthalate (BBP) and isodecyl phthalate (DIDP); dioctyl adipate (DOA), diisononyl adipate (DINA), dioctyl azelate (DOZ), dioctyl succinate (DOC), succinic acid Aliphatic carboxylates such as isodecyl (IDC), isodecyl sebacate (IDS) dibutyl sebacate (DBS) dioctyl sebacate (DOS), butyl oleate, tributyl acetylcitrate (ATBC); Glycol esters such as trile ester; Phosphate esters such as trioctyl phosphate and tricresyl phosphate; Epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate; Polyester plasticizers; Pinetal, linoleic acid, oleic acid Vegetable oils such as abietic acid, rapeseed oil, cottonseed oil, falling raw oil and palm oil; mineral oils such as extenders, process oils, paraffinic oils, naphthenic oils and aromatic oils; monoesters, epoxies, Examples thereof include synthetic plasticizers such as chlorinated paraffins, ethers, thioethers, polyesters, and polyethers.
These plasticizers may be used alone or in combination of two or more.

  Of these plasticizers, DINA and DINP are preferred. This is because the versatility is high, and it is inexpensive and easily available, and is excellent in compatibility with other compounds.

  10-40 mass% is preferable with respect to the total mass of a urethane prepolymer (A) and the said plasticizer, and, as for content of the plasticizer contained in the said main ingredient, 20-30 mass% is more preferable. On the other hand, 5-20 mass% is preferable with respect to the whole hardening | curing agent, and, as for content of the plasticizer contained in the said hardening | curing agent, 8-15 mass% is more preferable. If the content of the plasticizer is in the above range, the compatibility between the polybutadiene polyol and the polyether polyol and the compatibility between the main agent and the curing agent are further improved, and the physical properties of the cured product are lowered and the vinyl chloride adhesion is improved. Sexual decline does not occur.

In one preferred embodiment, the composition of the present invention contains calcium carbonate.
The calcium carbonate used in the composition of the present invention is not particularly limited, and specific examples thereof include heavy calcium carbonate, precipitated calcium carbonate (light calcium carbonate), colloidal calcium carbonate and the like. Moreover, the surface treatment calcium carbonate surface-treated with a fatty acid, a resin acid, a fatty acid ester, a higher alcohol addition isocyanate compound, etc. can also be used. Specifically, as calcium carbonate surface-treated with a fatty acid, whiten 305 (heavy calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd.), white gloss flower CCR (colloidal calcium carbonate, manufactured by Shiraishi Kogyo Co., Ltd.), Calfine 200 (colloidal calcium carbonate) , Manufactured by Maruo Calcium Co., Ltd.), calcium carbonate surface-treated with modified fatty acids, Ryton A-4 (heavy calcium carbonate, manufactured by Bihoku Powdered Industries Co., Ltd.), calcium carbonate surface-treated with fatty acid esters, Snowlite SS (Heavy calcium carbonate, manufactured by Maruo Calcium Co., Ltd.), Sealet 200 (Colloidal calcium carbonate, manufactured by Maruo Calcium Co., Ltd.) and the like are preferably used. Of these, those surface-treated with fatty acids, modified fatty acids, fatty acid esters, higher alcohol-added isocyanate compounds, and the like are particularly preferable. The surface-treated calcium carbonate contributes to shape retention and workability because the viscosity is increased, and contributes to storage stability because the surface is hydrophobic.
These may be used alone or in combination of two or more.

  The content of calcium carbonate is from 50 to 50 parts by mass with respect to a total of 100 parts by mass of the urethane prepolymer (A), the isocyanurate group-containing polyisocyanate (B) and the polyol (C) from the viewpoint of obtaining appropriate workability. The amount is preferably 80 parts by mass.

  The composition of the present invention is optionally provided with a filler other than calcium carbonate, a reaction retarding agent, an antioxidant, an antioxidant, a pigment (dye), and thixotropic modification, as long as the purpose of the present invention is not impaired. Various additives such as an agent, an ultraviolet absorber, a flame retardant, a solvent, a surfactant (including a leveling agent), a dispersant, a dehydrating agent, an adhesion-imparting agent, and an antistatic agent can be contained. These additives can be contained in one or both of the main agent and the curing agent.

  Examples of fillers other than calcium carbonate include organic or inorganic fillers of various shapes. Specifically, for example, fumed silica, calcined silica, precipitated silica, pulverized silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; magnesium carbonate, zinc carbonate; , Kaolin clay, calcined clay; carbon black; these fatty acid treated products, resin acid treated products, urethane compound treated products, and fatty acid ester treated products. The content of the filler is preferably 90% by mass or less in the entire composition in terms of physical properties of the cured product.

Specific examples of the anti-aging agent include hindered phenol compounds.
Specific examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).

  Specific examples of the pigment include inorganic pigments such as titanium oxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, etc .; azo pigment, phthalocyanine pigment, quinacridone Pigment, quinacridone quinone pigment, dioxazine pigment, anthrapyrimidine pigment, anthanthrone pigment, indanthrone pigment, flavanthrone pigment, perylene pigment, perinone pigment, diketopyrrolopyrrole pigment, quinonaphthalone pigment, anthraquinone pigment, thioindigo pigment, benzimidazolone Examples thereof include organic pigments such as pigments, isoindoline pigments, and carbon black.

Specific examples of the thixotropic agent include aerosil (manufactured by Nippon Aerosil Co., Ltd.), disparon (manufactured by Enomoto Kasei Co., Ltd.), and the like.
Specific examples of the adhesion-imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, and the like.

Specific examples of the flame retardant include chloroalkyl phosphate, dimethyl / methyl phosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, brominated polyether, and the like.
Examples of the antistatic agent generally include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

  The method for producing the composition of the present invention is not particularly limited. For example, the urethane prepolymer (A), the isocyanurate group-containing polyisocyanate (B) and optionally added plasticizers and additives may be added under reduced pressure or nitrogen. Under the inert gas atmosphere, the main agent obtained by sufficiently kneading and uniformly dispersing using a mixing apparatus such as a mixing mixer, and various additions such as polyol (C) and optionally added plasticizer and calcium carbonate It is obtained by kneading a curing agent containing an agent at the time of use.

  The composition of the present invention thus obtained is excellent in adhesion with vinyl chloride, particularly soft vinyl chloride, workability and underwater adhesion, and can suppress foaming during curing.

  The use of the composition of the present invention is not particularly limited, but the composition of the present invention is liquid and fluid, and is in an environment where a large amount of water exists (for example, outdoors during rain, wrinkles, underwater). Etc.) can also be cured. Therefore, since it can be spliced (constructed) at various locations, it can be used for a wide range of applications such as sealing materials and adhesives. In particular, from the point which has the outstanding characteristic as mentioned above, it can use suitably for the adhesion | attachment of the sheets in the composite sheet which consists of soft vinyl chloride.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
<Preparation of main ingredients 1-7>
Main agents 1 to 7 shown below were used as the first liquid.
Each polyol and plasticizer shown in Table 1 below were mixed in the proportions (parts by mass) shown in Table 1, this mixture was dehydrated at 110 ° C. under reduced pressure for 8 hours, and then diphenylmethane diisocyanate (MDI) was added to the mixture. ) Was added so that the NCO / OH molar ratio was 1.95, stirred in a nitrogen stream at 80 ° C. for 24 hours, and reacted to obtain each mixture containing a urethane prepolymer. . However, in Table 1 below, the addition amount of the plasticizer represents mass% with respect to the total mass of the obtained urethane prepolymer and the plasticizer (that is, the mass of each mixture).
Next, when the reaction rate of the above reaction (urethane prepolymer formation reaction) reached 100%, the amount shown in Table 1 was added to each mixture obtained to obtain the isocyanurate group-containing polyisocyanate (B). Each main ingredient was obtained by mixing. In addition, in the following Table 1, the addition amount of the isocyanurate group-containing polyisocyanate (B) represents a part by mass with respect to 100 parts by mass of the obtained urethane prepolymer (the addition amount of the plasticizer is not included hereinafter). Is. Moreover, NCO% represents the mass% of the NCO group with respect to the total mass of the prepolymer.

Each component shown in Table 1 is as follows.
Polybutadiene polyol: R45HT, number average molecular weight 2800, hydroxyl value 46.6 mg KOH / g, manufactured by Idemitsu Petrochemical Co., Ltd. Polyether polyol 1: D2000, number average molecular weight 2000, hydroxyl value 56 mg KOH / g, manufactured by Asahi Glass Co., Ltd. Polyether polyol 2: G8000G, number average molecular weight 8000, hydroxyl value 20.3 mgKOH / g, manufactured by Asahi Glass Co., Ltd. Castor oil-based polyol 1: Number average molecular weight 2000, hydroxyl value 50.4 mgKOH / g MDI (diphenylmethane diisocyanate) : Cosmonate PH, manufactured by Mitsui Takeda Chemical Co., Ltd. Plasticizer (diisononyl adipate): DINA, manufactured by Jay Plus Co., Ltd. Isocyanurate group-containing polyisocyanate (B) (HDI trimer): Takenate D170N, Takeshi Mitsui Ke Cal (Ltd.)

<Preparation of resin composition>
(Examples 1 and 2 , Reference Examples 1 to 3, Comparative Examples 1 to 6)
The above-mentioned main agents 1 to 7 and each component of the second liquid were blended in the composition (parts by mass) described in Table 2 below to prepare a resin composition.
In addition, content of the plasticizer which comprises the 2nd liquid of each resin composition in the following 2nd table | surface is the quantity from which the sum total with the plasticizer contained in a main ingredient will be 15 mass% with respect to the whole composition. It is. Further, the content of calcium carbonate constituting the second liquid of each resin composition is the sum of the urethane prepolymer and isocyanurate group-containing polyisocyanate (B) constituting each main component and the polyol constituting the second liquid. The amount is 70 parts by mass with respect to 100 parts by mass. In Table 2, “NCO / OH” means the total number of moles of NCO groups of the urethane prepolymer and isocyanurate group-containing polyisocyanate (B) constituting each main agent / OH of the polyol constituting the second liquid. The number of moles is shown.
About each obtained resin composition, the following vinyl chloride adhesiveness, foamability in water, compatibility of a main ingredient and a hardening | curing agent, workability | operativity, and underwater adhesiveness were evaluated. The results are shown in Table 2.

<PVC adhesiveness>
Each resin composition obtained was applied to a soft vinyl chloride sheet at a thickness of 5 mm and cured at 23 ° C. for 5 days to obtain a test specimen. Each specimen was subjected to a hand peeling test using a knife cut, and the peeled state was evaluated by CF (cohesive failure: the resin composition was broken) and AF (interface failure: broken at the interface between the soft PVC sheet and the resin composition). .

<Foaming properties in water>
Each composition obtained was poured into a container containing water and cured in water. A cross section of the obtained cured product was visually observed, and “◯” was obtained when there was almost no foaming, and “X” was obtained when foaming was confirmed.

<Compatibility between main agent and curing agent>
When the resin compositions shown in Table 2 below were cured, those cured without separation were designated as “◯”, and those separated into two layers were designated as “X”.

<Workability>
Each composition obtained had a viscosity of less than 300 ps as “◯”, and a high viscosity of 300 ps or more as “x”.

<Underwater adhesion>
Each obtained resin composition was applied to a soft vinyl chloride sheet placed in water (23 ° C.) at a thickness of 5 mm and cured for 5 days to give a test specimen. Each specimen was subjected to a hand peeling test using a knife cut, and the peeled state was evaluated by CF (cohesive failure: the resin composition was broken) and AF (interface failure: broken at the interface between the soft PVC sheet and the resin composition). .

Each component shown in Table 2 is as follows. The polybutadiene polyol, polyether polyol 1, polyether polyol 2, castor oil-based polyol 1 and plasticizer were the same as those shown in Table 1.
Polyether polyol 3: D4000, number average molecular weight 4000, hydroxyl value 30.6 mg KOH / g, manufactured by Asahi Glass Co., Ltd. Castor oil-based polyol 2: VRICY 202, hydroxyl value 120 mg KOH / g, manufactured by Ito Oil Co., Ltd. Calcium carbonate: Snow Light S, manufactured by Maruo Calcium Co., Ltd.

As is clear from the results in Table 2 above, the resin composition (Comparative Example 1) in which the main component urethane prepolymer does not have a polybutadiene skeleton is poorly compatible with the curing agent containing polybutadiene polyol, and is hydrophobic. Therefore, when cured in water, the water was entrained to cause foaming, and the adhesion in water was also low.
The resin composition (Comparative Example 2) in which the main component urethane prepolymer does not have a polybutadiene skeleton and the curing agent does not contain a polybutadiene polyol has low hydrophobicity, causes foaming when cured in water, and has an adhesive property in water. It was low.
The composition not containing the isocyanurate group-containing polyisocyanate (B) (Comparative Example 3) had low vinyl chloride adhesion and underwater adhesion.
The resin composition (Comparative Example 4), in which the polyol used as the raw material for the urethane prepolymer is only polybutadiene polyol and the polyol for the curing agent is also only polybutadiene polyol, has a high viscosity and poor workability, and also has a polyvinyl chloride adhesive property and an underwater adhesive property. It was low.
The resin composition (Comparative Example 5) having an NCO (main agent) / OH (curing agent) molar ratio as high as 1.3 and an excess of isocyanate groups causes foaming when cured in water, and exhibits adhesiveness in water. Was also low.
On the other hand, the resin compositions of Examples 1 and 2 were all excellent in polyvinyl chloride adhesion, foamability in water, compatibility between the main agent and the curing agent, workability, and in-water adhesion.

Claims (10)

A urethane prepolymer (A) obtained by reacting a polyisocyanate (b) with a polyol (a) containing 10 to 60% by mass of a polybutadiene polyol and 10 to 90% by mass of a polyether polyol, and an isocyanurate group-containing polyisocyanate ( B) and the content of the isocyanurate group-containing polyisocyanate (B) is 1 to 5% by mass with respect to the urethane prepolymer (A) ,
A curing agent containing a polyol (C) containing 10 to 50% by weight of a polybutadiene polyol, 10 to 80 % by weight of a polyether polyol and 80% by weight or less of a castor oil-based polyol ,
A two-component curable polyurethane resin composition having a molar ratio (NCO / OH) of an isocyanate group contained in the main agent to a hydroxy group contained in the curing agent of 0.8 to 1.05.   The polyol (a) further contains a castor oil-based polyol,
  2. The two-component curable polyurethane resin according to claim 1, wherein the polyol (a) contains 10 to 60 mass% of the polybutadiene polyol, 10 to 70 mass% of the polyether polyol, and 20 to 80 mass% of the castor oil-based polyol. Composition. The two-component curable polyurethane according to claim 1 or 2, wherein a molar ratio (NCO / OH) of an isocyanate group of the polyisocyanate (b) to a hydroxy group of the polyol (a) is 1.7 to 2.0. Resin composition. The two-component curable polyurethane resin composition according to any one of claims 1 to 3, wherein the main agent and / or the curing agent contains a plasticizer.   The two-component curable polyurethane resin composition according to any one of claims 1 to 4, wherein the isocyanate compound used in the isocyanurate group-containing polyisocyanate (B) is hexamethylene diisocyanate.   The two-component curable polyurethane resin composition according to any one of claims 1 to 5, wherein the polyisocyanate (b) is an aromatic polyisocyanate.   The two-component curable polyurethane resin composition according to any one of claims 1 to 6, wherein the polybutadiene polyol contained in the polyol (a) and the polyol (C) has a number average molecular weight of 1000 to 4000.   The total of the polybutadiene polyols contained in the polyol (a) and the polyol (C) is based on the total mass of the urethane prepolymer (A), the isocyanurate group-containing polyisocyanate (B) and the polyol (C). The two-part curable polyurethane resin composition according to any one of claims 1 to 7, which is 25 to 75% by mass.   Furthermore, calcium carbonate is contained, and the content of the calcium carbonate is 50 to 80 with respect to a total of 100 parts by mass of the urethane prepolymer (A), the isocyanurate group-containing polyisocyanate (B), and the polyol (C). The two-part curable polyurethane resin composition according to any one of claims 1 to 8, which is a mass part.   The two-component curable polyurethane resin composition according to any one of claims 1 to 9, which is used for bonding sheets in a composite sheet made of soft vinyl chloride.