JP6808970B2 - Coating material composition and its cured product - Google Patents

Description

The present invention relates to a curable resin composition preferably used as a coating material.

The curable resin composition used for coating materials such as flooring materials and waterproofing materials includes a one-component type that is cured by moisture in the air, a two-component type that is cured by mixing a curing agent such as polyol or polyamine, and latent. Examples include a 1.5-component type containing a sex curing agent, and examples of the main component for forming such a polyurethane composition include an NCO group-terminated urethane prepolymer obtained by reacting isocyanate and a polyol, a filler, and addition. A curable resin composition containing an agent is widely used, and as the polyol, for example, polytetramethylene glycol, polyester polyol, polyalkylene oxide and the like are used.

The curable resin composition using the polyester polyol has a high viscosity and tends to be inferior in handleability, and the polyurethane composition obtained by using the polyester polyol contains an ester group, so that the water resistance is inferior due to hydrolysis. There is a problem that the transition temperature (Tg) is high and the cold resistance is inferior.

On the other hand, the polyurethane composition using polytetramethylene glycol is excellent in hydrolysis resistance and cold resistance, and therefore can be suitably used in applications requiring such properties. However, polytetramethylene glycol is usually a solid in a room temperature environment, and when used, it is usually used by heating or dissolved in other components, and has a short pot life and is curable. The resin composition has a problem that it tends to be inferior in workability. Further, the polyurethane obtained by using it tends to have poor flexibility due to its crystallinity, and there is a problem that its use is limited.

Further, these polyols are generally limited to a molecular weight of about 4000, and it is difficult to increase the molecular weight, and there is a limit to imparting flexibility to the polyurethane composition obtained by using the same.

Polyalkylene oxides produced by addition polymerization of alkylene oxides such as propylene oxide are generally liquid and have a low viscosity, and curable resin compositions using such polyalkylene oxides are excellent in handleability and moldability.

Polyalkylene oxides are industrially produced by addition polymerization of alkylene oxides such as propylene oxide and ethylene oxide using an alkali metal such as potassium hydroxide as a catalyst.

However, when the polyalkylene oxide is produced by this method, the obtained polyalkylene oxide produces a large amount of monool and has a high degree of unsaturation. Therefore, a curable resin composition using such a polyalkylene oxide is used. Has a problem of inferior curability, and may require a long curing period due to the time required for curing, or may require an increase in the amount of catalyst, resulting in inferior storage stability of the composition. Further, there is a problem that it is difficult to obtain a uniform cured product by foaming due to moisture in the air and the workability is poor.

Further, the polyurethane composition using such a polyalkylene oxide having a high degree of unsaturation does not easily extend its molecular weight due to monool and contains a large amount of low molecular weight components, so that it easily bleeds from the urethane composition over time and contaminates the surroundings. Improvement was sought.

As a polyurethane using a polyalkylene oxide having a reduced degree of unsaturation, for example, a polyurethane obtained by reacting a polyalkylene oxide obtained by using cesium hydroxide or the like as a catalyst with a polyisocyanate compound has been proposed ( For example, see Patent Document 1). However, the degree of unsaturation of the polyalkylene oxide described in Patent Document 1 is still high, and the obtained polyurethane still does not exhibit sufficient curability and low contamination.

Further, a polyurethane obtained by reacting a polyalkylene oxide obtained by using a specific phosphazenium salt as a catalyst with a polyisocyanate compound has been proposed (see, for example, Patent Document 2). However, the degree of unsaturation of the polyalkylene oxide described in Patent Document 2 is still high, and it cannot be said that sufficient curability and low contamination are still exhibited.

As a polyalkylene oxide having a further reduced degree of unsaturation, a polyalkylene oxide obtained by using a compound metal cyanide complex as a catalyst is known (see, for example, Patent Document 3). However, the polyalkylene oxide described in Patent Document 3 has a problem such as poor handleability because it has a wide molecular weight distribution of about 1.1 and a high viscosity, and a curable resin composition using the polyalkylene oxide has a viscosity. There is a problem that it rises and is inferior in workability when it is applied as a floor material or a waterproof material, and there is a problem that gas generated by a reaction with moisture in the air is poorly released and easily foams.

Furthermore, since the polyurethane composition obtained by using the polyurethane composition tends to be non-uniform, improvement in contamination property and low tack property are not sufficient, and further improvement is required.

Japanese Unexamined Patent Publication No. 8-176263 JP-A-11-124424 Japanese Unexamined Patent Publication No. 4-59825

The present invention has been made in view of the above background techniques, and an object of the present invention is to provide a coating material having excellent workability, foam resistance, and curability, and a cured product thereof having low contamination.

As a result of diligent studies to solve the above problems, the present inventors have made an NCO group composed of a polyalkylene oxide unit and a polyisocyanate unit having a specific molecular weight distribution with a specific degree of unsaturation in a specific composition ratio. We have found that a composition containing a terminal urethane prepolymer can solve the above problems, and have completed the present invention.

That is, the present invention relates to the coating material composition shown below.

[1] One selected from the group consisting of an NCO group-terminated urethane prepolymer which is a reaction product of an active hydrogen-containing compound (A) and a polyisocyanate (B), a filler (C) and an additive (D). Alternatively, it is a curable resin composition containing two or more kinds.
The active hydrogen-containing compound (A) contains one or more polyalkylene oxides selected from the group consisting of bifunctional polyalkylene oxides (A1) and trifunctional or higher functional polyalkylene oxides (A2).
The more component of the bifunctional polyalkylene oxide (A1) and the trifunctional or higher functional polyalkylene oxide (A2) satisfies all of the following (a) to (d), and the NCO group-terminated urethane prepolymer is as follows. A coating material composition characterized by satisfying (e).
(A) The degree of unsaturation is 0.010 meq / g or less.
(B) The number average molecular weight calculated from the hydroxyl value (OHV) is 1000 or more.
(C) The molecular weight distribution (Mw / Mn) determined by the (GPC) method by gel permeation chromatography using polystyrene as a standard substance is 1.039 or less.
(D) The molecular weight distribution (Mw / Mn) obtained by the gel permeation chromatography (GPC) method and the number average molecular weight (M) calculated from the hydroxyl value (OHV) satisfy the following mathematical formula (1).

(E) The ratio (NCO / OH) of the total amount of NCO groups contained in the polyisocyanate (B) to the total amount of OH groups contained in the active hydrogen-containing compound (A) is 1.5 to 3.0 (molar ratio).

[2] The polyisocyanate (B) is polymethylene polyphenylene polyisocyanate (polymeric MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane. Diisocyanate, 1,5-naphthalenediocyanate, trizine diisocyanate, xylylene diisocyanate, 1,4-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, pentamethylene diisocyanate, 1,6-hexamethylene The composition according to the above [1], which is at least one selected from the group consisting of diisocyanates, these isocyanate-containing prepolymers, and modified products of these isocyanates.

[3] above [1 average functionality _{f ave} polyalkylene oxide (A1) and polyalkylene oxide (A2) and the combined polyalkylene oxide mixture, characterized in that in the range of 2.21 to 3.00 ] Or the composition according to any one of [2].

[4] The composition according to any one of the above [1] to [3], wherein the filler (C) contains one or more inorganic fillers.

[5] The additive (D) is characterized by containing one or more selected from the group consisting of a urethanization catalyst, a light stabilizer, an antioxidant, a plasticizer, and a solvent. The composition according to any one of [4].

[6] The molecular weight distribution (Mw / Mn) of the polyalkylene oxide obtained by the gel permeation chromatography (GPC) method using polystyrene as a standard substance is that four columns in which a separation column is filled with a filler having a particle size of 3 μm are provided. The composition according to any one of the above [1] to [5], wherein the composition is connected in series, a resistance tube is connected to the reference side, and the molecular weight distribution is analyzed under the condition that tetrahydrofuran is used as the developing solvent.

[7] A coating material made of a cured product of the composition according to any one of the above [1] to [6].

The coating material composition of the present invention has a low viscosity even when a polyalkylene oxide having a low degree of unsaturation is used, and is excellent in workability, foaming resistance, and curability.

Further, the coating material composed of a cured product of the coating material composition of the present invention has low tackiness, less bleeding after curing, and low contamination property, and is suitably used as a coating material used for flooring materials, waterproof materials, etc. it can.

The present invention will be described in detail below.

The coating material composition of the present invention comprises an NCO group-terminated urethane prepolymer which is a reaction product of an active hydrogen-containing compound (A) and a polyisocyanate (B), and a filler (C) and an additive (D). A curable resin composition containing one or more selected from the group.
The active hydrogen-containing compound (A) contains one or more polyalkylene oxides selected from the group consisting of bifunctional polyalkylene oxides (A1) and trifunctional or higher functional polyalkylene oxides (A2).
The more component of the bifunctional polyalkylene oxide (A1) and the trifunctional or higher functional polyalkylene oxide (A2) satisfies all of the following (a) to (d), and the NCO group-terminated urethane prepolymer is as follows. Its characteristic is to satisfy (e).
(A) The degree of unsaturation is 0.010 meq / g or less.
(B) The number average molecular weight calculated from the hydroxyl value (OHV) is 1000 or more.
(C) The molecular weight distribution (Mw / Mn) determined by the (GPC) method by gel permeation chromatography using polystyrene as a standard substance is 1.039 or less.
(D) The molecular weight distribution (Mw / Mn) obtained by the gel permeation chromatography (GPC) method and the number average molecular weight (M) calculated from the hydroxyl value (OHV) satisfy the above formula (1).
(E) The ratio (NCO / OH) of the total amount of NCO groups contained in the polyisocyanate (B) to the total amount of OH groups contained in the active hydrogen-containing compound (A) is 1.5 to 3.0 (molar ratio).

<Chemical composition of polyalkylene oxide>
In the present invention, the bifunctional polyalkylene oxide (A1) is not particularly limited, but for example, one or more active hydrogen-containing compounds R [-H] m are used, and the number of carbon atoms is 2 to 12. It is preferable that it is an alkylene oxide adduct to which one or more kinds of 3-membered ring alkylene oxides are added, and it is preferable that it is a polyalkylene oxide represented by the following general formula (1).

[In the above general formula (1), R is an m-valent group obtained by removing m active hydrogens from the active hydrogen-containing compound (R [−H] _m ), and Z is an alkylene group having 2 to 12 carbon atoms. Alternatively, it is a cycloalkylene group, and A is an alkylene group having 3 carbon atoms. When there are a plurality of Z or A, each may be the same or different. m is 2, p is an integer of 0 or 1 to 500, q is an integer of 1 to 1000, and r is an integer of 0 or 1 to 500. ]
Further, in the present invention, the trifunctional polyalkylene oxide (A2) is not particularly limited, but for example, one or more active hydrogen-containing compounds R [-H] m are used, and the number of carbon atoms is 2. It is preferably an alkylene oxide adduct to which one or more of the three-membered ring alkylene oxides of ~ 12 are added, and in the above general formula (1), R is an active hydrogen-containing compound (R [−H]. It is an m-valent group obtained by removing m active hydrogens from m), Z is an alkylene group having 2 to 12 carbon atoms or a cycloalkylene group, and A is an alkylene group having 3 carbon atoms (plural Z or If there is A, they may be the same or different), m is an integer of 3 to 100, p is an integer of 0 or 1 to 500, q is an integer of 1 to 1000, and r is an integer of 0 or 1 to 500. It is preferably an integer polyalkylene oxide.

Among these, a compound having an oxyalkylene group and having at least one active hydrogen group per molecule in a molecule at an arbitrary position such as a polymer terminal or a branched chain terminal is preferable.

The active hydrogen-containing compound (R [−H] _m ) is not particularly limited as long as it has an active hydrogen group, and is, for example, water, propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1, Bifunctional diols such as 6-hexanediol, tripropylene glycol, triethylene glycol and polyoxyalkylenediol, bisphenols such as bisphenol A, bisphenol F and bisphenol AD, dihydroxybenzenes such as catechol, resorcin and hydroquinone, methyl Examples thereof include compounds having two active hydrogen groups such as amines such as amines, ethylamines, propylamines and butylamines. As the active hydrogen-containing compound (R [−H] _m ), one or a mixture of two or more selected from these can be used.

The alkylene oxide to be added to the active hydrogen-containing compound (R [−H] _m ) may be a compound having one or more epoxy rings in the molecule, and is not particularly limited, but for example, ethylene oxide or propylene oxide. , Butylene oxide, styrene oxide and other alkylene oxides having 2 to 12 carbon atoms, and one or more kinds of alkylene oxides may be used.

Among these, one or more alkylene oxides containing alkylene oxides having 2 to 3 carbon atoms such as propylene oxide and ethylene oxide, which are easily available industrially, are preferable, and one or more alkylene oxides containing propylene oxide are preferable. Ethylene oxide is more preferred.

Since the ZO in the general formula (1) tends to have a low viscosity and easily exhibits good urethane moldability, it is a poly derived from an alkylene oxide having 2 to 12 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, and styrene oxide. It preferably has an ether structure. More preferably, it is a one-type or two or more kinds of alkylene oxide-derived polyether structure selected from ethylene oxide and propylene oxide, and most preferably a kind of polyether structure selected from ethylene oxide and propylene oxide.

In the general formula (1), p is an integer of 0 or 1 to 500, preferably an integer of p = 0 or 1 to 100, and more preferably p = 0.

Examples of Z in the general formula (1) include a structure represented by the following general formula (2).

[In the above general formula (2), R ₂ , R ₃ , R ₄ , and R ₅ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a cycloalkyl having 3 to 10 carbon atoms. However, the total number of carbon atoms of R _{2 to} R ₅ does not exceed 10. It is also possible to form any two members to cycloalkyl group R ₂ to R _5. ]
Further, the AO in the general formula (1) has a polyether structure derived from an alkylene oxide having 3 carbon atoms such as propylene oxide because the viscosity tends to be low and good mechanical properties are easily exhibited when polyurethane is used. Is preferable.

Examples of A in the general formula (1) include a structure represented by the following formula.

Q in the general formula (1) is an integer of 1 to 1000, preferably an integer of q = 10 to 500, and more preferably an integer of q = 15 to 250.

R in the general formula (1) is an integer of 0 or 1 to 500. Since it is difficult to solidify at a low temperature and is easy to handle, it is preferably r = 0 or an integer of 1 to 90, and more preferably r = 0.

The relationship between p, q, and r in the general formula (1) is p + q> r (however, p + q is 10 to 1000, q) because the viscosity tends to be low and good mechanical properties are likely to be exhibited when polyurethane is used. Is preferably 10 to 1000 and r is 0 or 1 to 90). More preferably, it satisfies p + q> 5r (where p + q is 30 to 600, q is 30 to 500, r is 0 or 1 to 90), and most preferably p + q> 10r (where p + q is 50 to 600, q). Is 50 to 500, and r is 0 or 1 to 90).

As the polyalkylene oxide (A1), m in the above general formula (1) is 2. The polyalkylene oxide (A2) is not particularly limited as long as m in the general formula (1) is in the range of 3 to 100, but is preferably in the range of 3 to 5.

When the polyalkylene oxide (A1) and the polyalkylene oxide (A2) are used in combination, the molecular weight distribution tends to be narrow and the handleability is easy to be excellent. Therefore, the polyalkylene oxide (A) is preferably a diol or poly having m = 2. A combination of triols with an alkylene oxide (B) of m = 3.

When the polyalkylene oxide (A1) and the polyalkylene oxide (A2) are used in combination, it is more preferable that each of the polyalkylene oxide (A) and the polyalkylene oxide (B) has the above structure, but it is contained. If the molecular structure of the polyalkylene oxide having the larger amount has the above structure, it can be preferably used.

<Molecular weight distribution of polyalkylene oxide>
When bifunctional polyalkylene oxide (A1) is used alone as the active hydrogen-containing compound (A), its molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) using polystyrene as a standard substance. ) Is 1.039 or less. It is preferably in the range of 1.003 to 1.029, more preferably in the range of 1.005 to 1.019, and most preferably in the range of 1.006 to 1.016.

When trifunctional polyalkylene oxide (A2) is used alone as the active hydrogen-containing compound (A), its molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) using polystyrene as a standard substance. ) Is not particularly limited, but is preferably 1.069 or less. It is more preferably in the range of 1.003 to 1.039, and even more preferably in the range of 1.005 to 1.019.

Furthermore, when a bifunctional polyalkylene oxide (A1) and a trifunctional or higher functional polyalkylene oxide (A2) are used in combination as the active hydrogen-containing compound (A), gel permeation chromatography (GPC) using polystyrene as a standard substance. The molecular weight distribution (Mw / Mn) of each of the polyalkylene oxide (A1) and the polyalkylene oxide (A2) determined by the method) is more preferably within the above range, but the polyalkylene oxide having the larger content If the molecular weight distribution (Mw / Mn) is within the above range, it can be preferably used.

When this molecular weight distribution (Mw / Mn) exceeds 1.039, in addition to the increase in viscosity, which is considered to be due to the increase in high molecular weight components and the decrease in monool, the deterioration of curability, which is considered to be due to the influence of low molecular weight components, is caused. It is easy to cause, and when a curable resin composition using it is used for coating materials such as flooring materials and waterproof materials, it is difficult for air bubbles to escape, resulting in poor workability and poor productivity, and air bubbles generated during curing are also present. Since it is viscous, it does not come off and tends to be inferior in foam resistance.

In particular, when the molecular weight distribution (Mw / Mn) of the polyalkylene oxide (A1) exceeds 1.039, or when the degree of unsaturation described later exceeds 0.029 meq / g, the handleability in bulk is poor. Furthermore, the miscibility of the filler and additives also deteriorates, and when the reaction or composition becomes non-uniform or the reaction becomes non-uniform, the polyurethane cured product obtained by using such a curable resin composition has a low molecular weight. Since it is easy to cause contamination of the substrate by components and the like, the polyalkylene oxide (A1) is preferably in the range of less than 20 parts by weight with respect to 100 parts by weight of the polyalkylene oxide (A2), and in the range of less than 10 parts by weight. It is more preferable to have.

When the molecular weight distribution (Mw / Mn) of the polyalkylene oxides (A1) and (A2) is 1.029 or less, a remarkable viscosity reducing effect is obtained, the bulk handling property is improved, and the additives are mixed. The properties are also good, and the reaction and composition tend to be uniform.

When bifunctional polyalkylene oxide (A1) or trifunctional or higher functional polyalkylene oxide (A2) is used alone as the active hydrogen-containing compound (A), gel permeation chromatography (GPC) using polystyrene as a standard substance. The relationship between the molecular weight distribution (Mw / Mn) obtained by the method and the number average molecular weight (M) calculated from the polystyrene value (OHV) described later satisfies the above formula (1).

It is preferable to satisfy the following mathematical formula (2).

More preferably, the following mathematical formula (3) is satisfied.

When a bifunctional polyalkylene oxide (A1) and a trifunctional or higher functional polyalkylene oxide (A2) are used in combination as the active hydrogen-containing compound (A), the polyalkylene oxide (A1) and the polyalkylene oxide (A2) are used. It is preferable that each of them satisfies the above formula, but if the polyalkylene oxide having a higher content satisfies the above formula, it can be preferably used.

The molecular weight distribution (Mw / Mn) obtained by the gel permeation chromatography (GPC) method using polystyrene as a standard substance is obtained by connecting four columns in which a separation column is filled with a filler having a particle size of 3 μm in series for the reason described later. However, it is preferable that the molecular weight distribution is measured and analyzed under the condition that a resistance tube is connected to the reference side and tetrahydrofuran is used as the developing solvent, and the molecular weight distribution calculated by using a cubic approximation curve calibration curve using standard polystyrene. It is desirable that it is (Mw / Mn).

The number of separation columns is preferably 3 to 5, and is particularly preferable, because the separation ability (theoretical plate number) is high and it is easy to suppress the spread of the molecular weight distribution due to fluctuations in the baseline and minute peaks of impurities in the liquid. There are four.

The particle size of the packing material of the separation column is preferably 1 to 4.5 μm because the measurement time is appropriate and it is easy to suppress the expansion of the molecular weight distribution due to fluctuations in the baseline and minute peaks of impurities in the liquid. Particularly preferably, it is 3 μm.

The exclusion limit of the separation column is preferably 50,000 to 3 million, more preferably 60,000 to 400,000. The inner diameter of the separation column is preferably 5 to 7.5 mmφ, more preferably 6 mmφ. The length of the separation column is preferably 10 to 25 cm, more preferably 15 cm.

Examples of such a separation column include Tskgel Super H4000 and Tskgel Super H3000 manufactured by Tosoh Corporation. The most preferable configuration of the separation column is a configuration in which a total of four Tskgel SuperH4000 × 2 and Tskgel SuperH3000 × 2 manufactured by Tosoh are connected in series.

The flow rate on the separation column side is preferably 0.5 to 0.9 ml / min, and more preferably 0.6 ml / min. The column temperature is preferably 30 ° C. to 50 ° C., more preferably 40 ° C.

Further, since it is easy to suppress the spread of the molecular weight distribution due to the pulsation of the pump on the reference side, it is preferable to connect 2 to 6 resistance tubes, more preferably 5 resistance tubes, and most preferably. It is a connection of 5 resistance tubes and 1 separation column.

As the resistance tube, a tube having a length of 2 m and an inner diameter of 0.1 mmφ is preferable.

The flow velocity on the reference side is preferably 0.1 to 0 in the state of five resistance tubes because the pulsation cycle of the pump is short and it is easy to suppress the fluctuation of the baseline and it is easy to suppress the expansion of the molecular weight distribution due to the pulsation of the pump. It is 6 ml / min, more preferably 0.15 ml / min.

The polystyrene used as the standard substance for the cubic approximate curve calibration curve is preferably 6 to 10 points, and more preferably 8 points. The molecular weight of polystyrene used in a standard substance having a known molecular weight is preferably selected from the range of 300 to 3000000, and more preferably selected from the range of 450 to 1100000. Specifically, for example, selection of 8 points of 500, 1010, 2630, 10200, 37900, 96400, 427000, 1090000 and the like can be mentioned, and measurement of the standard substance includes 4 points of 500, 2630, 37900, 427000 and 1010, 10200. It may be measured in two steps such as 4 points of 96400 and 1090000.

The developing solvent is preferably dimethylformamide or tetrahydrofuran, and more preferably BHT stabilizer-containing special grade tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd.

The sample concentration is preferably 0.5 to 2 mg / ml, more preferably 1 mg / ml. The injection amount of the sample solution is preferably 10 to 90 μl, in which the peak is less likely to be broad and the molecular weight distribution is less likely to spread, and more preferably 20 μl.

The area ratio of the low molecular weight component in the gel permeation chromatography (GPC) method is preferably 4.5% or less of the entire peak, and more preferably 2% or less. The viscosity tends to increase as the area ratio of the low molecular weight component decreases, but it is preferable to use a polyurethane elastomer because it has few transition components and is easily excellent in handleability and mechanical properties.

In the present invention, the area ratio of the low molecular weight components of the polyalkylene oxides (A1) and (A2) in the gel permeation chromatography (GPC) method is preferably 4.5% or less of the total peak, and is 2%. The following is more preferable. The viscosity tends to increase as the area ratio of the low molecular weight component decreases, but polyurethane is preferable because it has few transition components and is easily excellent in handleability and mechanical properties.

Here, the "area ratio of low molecular weight components" in the gel permeation chromatography (GPC) method is calculated when measuring the molecular weight distribution by the gel permeation chromatography (GPC) method using polystyrene as a standard substance. It refers to a low molecular weight component with a number average molecular weight of 1/3 or less of the number average molecular weight (Mn), and peaks at a point of 1/3 of the number average molecular weight (Mn) calculated when measuring the baseline and molecular weight distribution. The area% of the low molecular weight component can be obtained by dividing.

<Characteristics of polyalkylene oxide>
When a bifunctional polyalkylene oxide (A1) or a trifunctional or higher functional polyalkylene oxide (A2) is used alone as the active hydrogen-containing compound (A), the degree of unsaturation is 0.010 meq / g or less. .. It is preferably in the range of 0.002 to 0.009 meq / g, and more preferably in the range of 0.004 to 0.008 meq / g.

When a bifunctional polyalkylene oxide (A1) and a trifunctional or higher functional polyalkylene oxide (A2) are used in combination as the active hydrogen-containing compound (A), the polyalkylene oxide (A1) and the polyalkylene oxide (A2) are used. It is preferable that each degree of unsaturation is within the above range, but it can be preferably used as long as the degree of unsaturation of the polyalkylene oxide having a higher content is within the above range.

Polyurethane obtained by using a polyalkylene oxide having a high degree of unsaturation exceeding 0.010 meq / g does not cure well and a large amount of migration components are generated, resulting in poor stain resistance, and it takes time to cure and workability is required. It is difficult to use due to the deterioration of. Furthermore, a large amount of low molecular weight monool is produced as a by-product, which causes a decrease in the number average molecular weight, which makes it difficult to increase the molecular weight of the polyalkylene oxide and also makes it difficult to obtain a polyalkylene oxide having a narrow molecular weight distribution. ..

In the present invention, the "unsaturation degree (meq / g)" of the polyalkylene oxide is the total amount of unsaturated groups contained in 1 g of the polyalkylene oxide, and is the method specified in JIS K1557 6.7. It is a value measured according to. The degree of unsaturation of polyalkylene oxide is an index of the amount of monool present in polyalkylene oxide, and the viscosity decreases as it increases, but the average number of functional groups of polyalkylene oxide may decrease, so it is used as a raw material for polyurethane. At that time, a termination reaction may occur, leading to a decrease in the molecular weight of the polyurethane and an increase in uncrosslinked low molecular weight components, or acting as a dungling chain in the polyurethane, which may reduce the curability.

In the present invention, the number average molecular weight (M) calculated from the OHV of the more component of the polyalkylene oxide (A1) or the polyalkylene oxide (A2) is 1000 or more. It is preferably in the range of 2000 to 30000, more preferably in the range of 2000 to 15000, and most preferably in the range of 2000 to 7500.

When the number average molecular weight (M) of the larger component of the polyalkylene oxide (A1) or the polyalkylene oxide (A2) is less than 1000, the difference in the degree of unsaturation and the molecular weight distribution becomes small, and the curable resin composition is applied. The remarkable effect of improving the property and improving the contamination of the cured product cannot be obtained.

On the other hand, the number average molecular weight (M) calculated from the OHV of the polyalkylene oxide (A2) is not particularly limited, but is preferably in the range of 2000 to 30000, more preferably in the range of 2000 to 15000, and most preferably in the range of 2000 to 15000. Is in the range of 2000-7500.

In the present invention, the number average molecular weight (M) calculated from the OHV of the polyalkylene oxide is a value calculated using the following mathematical formula (4) based on the hydroxyl value (OHV, unit is mgKOH / g) of the polyalkylene oxide. Say.

Here, "OHV" is a value measured in accordance with JIS K1557 6.4. The "number of hydroxyl groups per molecule" refers to the number of active hydrogen atoms per molecule of the active hydrogen-containing compound, which is an initiator used as a raw material in producing the polyalkylene oxide (A). If the number of active hydrogen atoms in the initiator cannot be specified in a commercially available product, the nominal number of functional groups is used.

In the present invention, the polyalkylene oxide (A1) used as the active hydrogen-containing compound (A) is a liquid in a room temperature environment, and an amorphous compound is preferable. If it is liquid and amorphous in a room temperature environment, it is easy to use without heating and has excellent moldability.

Further, the glass transition temperature of the polyalkylene oxide (A1) is preferably −30 ° C. or lower because the low temperature characteristics of the obtained curable resin composition tend to be excellent because of its excellent handleability.

The viscosity of the polyalkylene oxide (A) used as the active hydrogen-containing compound (A) under 25 ° C. conditions is not particularly limited and may be appropriately selected depending on the intended use, but is preferably 0.1 to 2000 Pa · s (25 ° C.). It is in the range, more preferably 0.2 to 200 Pa · s (25 ° C.). If the viscosity of the polyalkylene oxide (A) is in the range of 0.1 to 2000 Pa · s (25 ° C.), it is easy to mold and it is easy to control the physical properties of the cured product.

In the present invention, the "viscosity" under the condition of 25 ° C. refers to a value measured by a cone plate rotational viscometer according to JIS K1557-5 6.2.3. Specifically, it refers to the viscosity under the condition of a shear rate of 0.1 (1 / s), but if the viscosity does not fall within the measurement range, the shear rate range is set to 0.01 to 10 (1 / s) so as to fall within the measurement range. ) May be adjusted.

In the present invention, when the polyalkylene oxide (A1) and the polyalkylene oxide (A2) are used in combination as the active hydrogen-containing compound (A1), the amount of the polyalkylene oxide (A1) added is as long as the gist of the present invention is not impaired. Although not particularly limited, it is preferably in the range of 0.5 to 100 parts by weight, and more preferably in the range of 0.5 to 80 parts by weight with respect to 100 parts by weight of the polyalkylene oxide (A1). Among them, when the degree of unsaturation of the polyalkylene oxide (A2) exceeds 0.029 meq / g, or when the molecular weight distribution exceeds 1.069, the polyalkylene oxide (A2) is based on 100 parts by weight of the polyalkylene oxide (A1). ) Is preferably in the range of 0.5 to 20 parts by weight, most preferably in the range of 0.5 to 10 parts by weight.

When the polyalkylene oxide (A1) and the polyalkylene oxide (B) are used in combination as the active hydrogen-containing compound (A), a polyalkylene oxide mixture obtained by combining the polyalkylene oxide (A1) and the polyalkylene oxide (A2). it is preferred that the average functionality _{f ave} is in the range of 2.21 to 3.00. Average the value of the functional groups _fave is too low, the abrasion resistance tends to decrease in the elastic modulus of the coating material is decreased, also not follow the expansion and contraction of too high undercoat and topcoat waterproof deterioration or cracks The range is preferably in the range of 2.21 to 2.80, and more preferably in the range of 2.29 to 2.49.

In the present invention, the average number of functional groups _fave as a polyalkylene oxide mixture obtained by combining the polyalkylene oxide (A1) and the polyalkylene oxide (A2) is a value calculated from the following formula (5).

_{Here, f A1} is average functionality polyalkylene oxide _{(A1), W} A1 is parts by weight of polyalkylene oxide _{(A1), M} A1 represents a number average molecular weight of the polyalkylene oxide _{(A1), f A2} poly average functionality of the alkylene oxide _{(A2), W} A2 is parts by weight of the alkylene oxide _{(A2), M} A2 represents a number average molecular weight of the polyalkylene oxide (A2).

The average number of functional groups of the present invention does not take into account the substantial decrease in the number of functional groups due to the by-produced monool, and the diol obtained by using the bifunctional initiator is obtained by using a few functional initiators. The resulting triol can be calculated as 3.

Further, as the active hydrogen-containing compound (A), polyalkylene oxide (A1), such as polytetramethylene glycol, polyester polyol, chain extender such as low molecular weight diol and low molecular weight diamine, as long as the gist of the present invention is not impaired, Other active hydrogen-containing compounds other than A2) may be contained. The content of the other active hydrogen-containing compound is preferably less than 50 parts by weight with respect to 100 parts by weight of the polyalkylene oxide having a larger content among the polyalkylene oxides (A1) and (A2). It is preferably in the range of less than 5 parts by weight, and most preferably not contained.

<Manufacturing of polyalkylene oxide>
In the present invention, the method for producing the polyalkylene oxide (A1) is not particularly limited, but for example, ring-opening polymerization of the alkylene oxide is carried out in the presence of an active hydrogen-containing compound, a base catalyst and a Lewis acid. Can be manufactured by

For example, when an active hydrogen-containing compound and a base catalyst are mixed and treated under reduced pressure to prepare a catalytically active species precursor, sufficient water and solvent are removed.
Furthermore, when Lewis acid is mixed and treated under reduced pressure to prepare a catalytically active species, by-products are sufficiently removed, and by selecting a specific Lewis acid that is a by-product with a low boiling point, it is a factor to widen the molecular weight distribution. Suppressing the polyalkylene oxide derived from Lewis acid,
Through the manufacturing process of adding an alkylene oxide using a catalyst that combines a base catalyst with few side reactions and a specific Lewis acid,
Use alkylene oxides with a low water content of 100 ppm or less,
However, the production is not particularly limited.

The method for producing the polyalkylene oxide (A2) is not particularly limited, and the polyalkylene oxide (A2) can be produced by a conventionally known production method. For example, an alkylene oxide is added to a trifunctional or higher functional initiator to a predetermined molecular weight using a cesium metal compound catalyst, a composite metal cyanide complex catalyst, a phosphazene catalyst, an imino group-containing phosphazenium salt catalyst, a barium hydroxide catalyst, or the like. There is a way to do it.

A low-viscosity polyalkylene oxide (A2) having a low degree of unsaturatedness and a narrow molecular weight distribution can be easily obtained, and the curable resin composition containing a urethane prepolymer using the polyalkylene oxide (A2) can be easily handled and the obtained cured urethane product can be improved. Since it tends to have excellent stain resistance, it is preferably produced by ring-opening polymerization of an alkylene oxide in the presence of an active hydrogen-containing compound, a base catalyst such as an imino group-containing phosphazenium salt, and a Lewis acid catalyst.

The base catalyst is not particularly limited, but it is preferable to use a catalyst system in which a base catalyst and a Lewis acid are used in combination because the applicable range of the alkylene oxide is wide, the polymerization activity is high, and the degree of unsaturation tends to be low.

Here, the Lewis acid is not particularly limited, and examples thereof include an aluminum compound, a zinc compound, and a boron compound. Among these, organoaluminum, aluminoxane, and organozinc are preferable, and organoaluminum is more preferable, because it is an alkylene oxide polymerization catalyst having excellent catalytic performance.

Examples of the aluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, trinormalhexylaluminum, triethoxyaluminum, triisopropoxyaluminum, triisobutoxyaluminum, triphenylaluminum, diphenylmonoisobutylaluminum, monophenyldiisobutylaluminum and the like. Organic aluminum; aluminoxane such as methylaluminoxane, isobutylaluminoxan, methyl-isobutylaluminoxan; inorganic aluminum such as aluminum chloride, aluminum hydroxide, aluminum oxide can be mentioned.

Among these, trimethylaluminum, triethylaluminum, which have a low boiling point of 100 ° C. or less and are easy to remove when preparing catalytically active species and easily suppress polyalkylene oxide derived from Lewis acid, which is a factor to widen the molecular weight distribution. Triisobutylaluminum, trinormalhexylaluminum, triethoxyaluminum, triisopropoxyaluminum and the like are preferable. The compound produced as a by-product during the preparation of catalytically active species can be determined from the structure of Lewis acid. For example, in trimethylaluminum, methane in which H is added to the methyl group of the substituent on aluminum, and in triisobutylaluminum, isobutyl of the substituent on aluminum. Isobutane with H added to the group and triisopropoxyaluminum are isopropanol with H added to the isopropoxy group.

Examples of the zinc compound include organic zinc such as dimethyl zinc, diethyl zinc and diphenyl zinc; and inorganic zinc such as zinc chloride and zinc oxide.

Examples of the boron compound include triethylborane, trimethoxyborane, triethoxyborane, triisopropoxyborane, triphenylborane, tris (pentafluorophenyl) borane, trifluoroborane and the like.

The base catalyst is not particularly limited, but a base compound having a PN bond is desirable. More preferably, it is a base compound having an imino group and a PN bond, and examples thereof include an iminophosphazenium salt compound represented by the following general formula (3) (see, for example, JP-A-2011-132179). ..

[In the above general formula (3), R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ₁ and R ₂ may be bonded to each other to form a ring structure, or R ₁ may be bonded to each other or R ₂ may be bonded to each other to form a ring structure. X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, or a hydrogen carbonate anion. ]
The ratio of the base catalyst to Lewis acid is not particularly limited and is arbitrary as long as the action as an alkylene oxide polymerization catalyst is exhibited. For example, the base catalyst: Lewis acid = 1: 0.002 to 500 (mol). Ratio).

The polymerization temperature at the time of producing the polyalkylene oxide used in the present invention is not particularly limited, but is in the range of 70 to 150 ° C. because the polyalkylene oxide is decomposed and the molecular weight distribution is difficult to spread and the catalytic activity is easily exhibited. It is preferably, more preferably in the range of 90 to 110 ° C.

The polymerization pressure for producing the polyalkylene oxide used in the present invention is not particularly limited, but is in the range of 0.05 to 1.0 MPa, preferably 0.1 to 0.6 MPa.

The stirring speed at the time of producing the polyalkylene oxide used in the present invention is not particularly limited and depends on the shape and internal volume of the polymerization vessel, the shape of the stirring blade, etc., but a cylindrical polymerization vessel having an internal volume of 2 L and an anchor type. In the case of a stirring blade, it is preferable to sufficiently stir at 300 rpm or more.

When adding an alkylene oxide to an active hydrogen-containing compound using a catalyst that combines an iminophospazenium salt and a Lewis acid, the iminophospazenium salt (including its precursor), Lewis acid, and an active hydrogen-containing compound At the same time, a method of preparing a catalytically active species by heating and depressurizing treatment, etc., and a method of mixing one of these components with the other two components and performing heating and depressurizing treatment, etc. to prepare a catalytically active species. , A method of preparing a catalytically active species by mixing two of these components with the other one component and performing heat / decompression treatment, etc., and mixing two of these components and performing heat / decompression treatment, etc. to perform catalytic activity. Any method may be used, such as a method in which the seed precursor is prepared, the other one component is mixed, and further heating / reducing pressure treatment is performed to prepare a catalytically active species. Of these, by-products and impurities are easily removed, and a polyalkylene oxide having a narrow molecular weight distribution is easily obtained. Therefore, preferably, an iminophosphazenium salt and an active hydrogen-containing compound are mixed and then heated and depressurized. After that, it is preferable to go through a production process in which Lewis acid is mixed and further heated / reduced pressure treatment is performed to prepare a catalytically active species and alkylene oxide is added.

The temperature of the heating / depressurizing treatment at that time is preferably 100 ° C. or higher, more preferably 100 to 130 ° C., because by-products and impurities are easily removed and a polyalkylene oxide having a narrow molecular weight distribution can be easily obtained. The pressure during the heating / depressurizing treatment is preferably less than 0.5 kPa, more preferably 0.001 to 0.2 kPa, because by-products and impurities are easily removed and a polyalkylene oxide having a narrow molecular weight distribution can be easily obtained. is there. The time for the heating / depressurizing treatment at that time varies depending on the shape of the reaction vessel and the like, but it is 2 hours or more after mixing the iminophosphazenium salt and / or its precursor, Lewis acid, and the active hydrogen-containing compound. Preferably, more preferably, iminophosphazenium salt and / or a precursor thereof and an active hydrogen-containing compound are added to heating and distillation under reduced pressure for 2 hours or more after mixing, and after mixing with Lewis acid, further heating and distillation under reduced pressure for 2 hours or more. It is preferable to do so. Further, in order to remove impurities, a dehydrating solvent having a low boiling point may be added and an azeotropic operation may be performed to remove impurities.

The polyalkylene oxide used in the present invention is not particularly limited, but is preferably one in which the catalyst is removed after polymerization because the viscosity may increase if the catalyst remains. The amount of the catalyst residue of the polyalkylene oxide is preferably 200 ppm or less, more preferably 100 ppm or less. Here, the amount of catalyst residue refers to the total amount of catalyst residue when two or more types of catalysts are used in combination.

<Polyisocyanate>
In the present invention, the polyisocyanate (B) is not particularly limited, and examples thereof include compounds having at least two isocyanate groups.

Specifically, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalenedi isocyanate, trizine diisocyanate, xylylene diisocyanate. , 1,3-phenylenediocyanate, 1,4-phenylenediocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1 , 4-Cyclohexanediisocyanate, 1,4-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, pentamethylene diisocyanate, norbornandiisocyanate, lysine ester triisocyanate, 1,6,11-undecantry Isocyanates, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate, isocyanate-containing prepolymers produced by the reaction between them and polyols, and these. A mixture of two or more kinds is exemplified. Further, modified products of these isocyanates (for example, modified products containing urethane group, carbodiimide group, allophanate group, urea group, burette group, isocyanurate group, amide group, imide group, uretonimine group, uretdione group or oxazolidone group) and Condensations such as polymethylene polyphenylene polyisocyanate (Polymeric MDI) (sometimes referred to as polynuclears) are also included.

Among these, polymethylene polyphenylene polyisocyanate (polymeric MDI), 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate, because it is easy to obtain a curable resin composition having excellent productivity and curability. Isocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalenediocyanate, trizine diisocyanate, xylylene diisocyanate, 1,4-bis (isocyanatomethyl) cyclohexane, 1,3-bis ( Isocyanatomethyl) cyclohexane, pentamethylene diisocyanate, prepolymers containing these isocyanate groups, modified products of these isocyanates (eg, urethane group, carbodiimide group, allophanate group, urea group, burette group, isocyanurate group, amide group, An imide group, a uretonimine group, a uretdione group or an oxazoridone group-containing modified product) and the like are preferable. These isocyanates may be used alone or in admixture of two or more.

In addition, because of its excellent flexibility, 1,6-hexamethylene diisocyanate and modified products of these isocyanates (for example, urethane group, carbodiimide group, allophanate group, urea group, burette group, isocyanurate group, amide group, imide group) , Uretonimine group, uretdione group or oxazolidone group-containing modified product) and the like can be preferably used. These isocyanates may be used alone or in admixture of two or more.

Examples of the isocyanate-containing prepolymer include a reaction product of a monool such as polyoxyalkylene monoalkyl ether, isotridecanol, hexyldecanol, ethylhexanol, and butyltetraglycol, a polyol, a monoamine, or a polyamine with the corresponding isocyanate. Can be mentioned.

The number of functional groups of the polyisocyanate (B) (the number of NCO functional groups in one molecule) is not particularly limited, but is preferably 2 to 6 functional, and more preferably 2 to 4 functional.

As the addition amount of the polyisocyanate (B), the ratio of the total amount of NCO groups contained in the polyisocyanate (B) to the total amount of OH groups contained in the active hydrogen-containing compound (A) (described as NCO / OH ratio) is 1.5 to 3. It is in the range of 0.0. The coating material is more preferably in the range of 1.7 to 2.5, and the range of 1.7 to 2.0 is particularly preferable because free isocyanates that deteriorate the working environment such as free TDI are less likely to be generated.

If the NCO / OH ratio is less than 1.5, the coating material used as the floor material / waterproof material does not have appropriate elasticity, and tackiness is likely to be exhibited, which may make it difficult to use. Further, in the range where the NCO / OH ratio exceeds 3.0, the coating material has poor followability to the substrate, cracks occur, and good waterproofness and the like are not exhibited, so that it is difficult to use.

Further, if the NCO / OH ratio is less than 1.5, the curable resin composition may become thickened and cannot be normally handled as a coating material composition for a floor material or a waterproof material, making it difficult to use. Further, if the NCO / OH ratio is less than 1.0, curing is insufficient, which may make it difficult to use for the purpose. Further, if the NCO / OH ratio exceeds 3.0, the amount of polyisocyanate monomer liberated increases, which may worsen the working environment, which may make it difficult to use.

The amount of the polyisocyanate (B) used is not particularly limited as long as it does not impair the gist of the present invention, but is preferably the polyalkylene oxide (A1) or (A2) having the larger content. It is in the range of 0.5 to 200 parts by weight, more preferably 5 to 70 parts by weight, and most preferably 10 to 50 parts by weight with respect to 100 parts by weight of the oxide.

<NCO group-terminated urethane prepolymer>
In the present invention, the NCO group-terminated urethane prepolymer used in the curable resin composition is, for example, an NCO group-terminated urethane prepolymer which is a reaction product of the above-mentioned active hydrogen-containing compound (A) and polyisocyanate (B). Examples thereof include compounds having one or more of. Its properties are preferably liquid.

In the present invention, the content of the NCO group-terminated urethane prepolymer in the curable resin composition is not particularly limited, but is in the range of 20 to 99.9% by weight in the main agent of the curable resin composition. It is preferably in the range of 20 to 80% by weight, more preferably in the range of 20% by weight to 60% by weight.

In the present invention, the number average molecular weight of the NCO group-terminated urethane prepolymer in terms of standard polystyrene is not particularly limited, but is preferably in the range of 1000 to 100,000 because it has an appropriate viscosity and is easy to handle. More preferably, it is in the range of 1000 to 40,000. Here, the number average molecular weight in terms of standard polystyrene is measured by GPC (gel permeation chromatography) under the conditions of a column temperature of 40 ° C., a flow velocity of 1.0 ml / min, and a solvent THF, and is a third-order approximation using standard polystyrene. It can be calculated as a curve calibration curve.

In the present invention, the viscosity of the NCO group-terminated urethane prepolymer is not particularly limited, but since the workability tends to be good, 1000 to 200,000 mPa. The range is preferably in the range of s, more preferably in the range of 3000 to 100,000 mPa · s.

In the present invention, the method for synthesizing the NCO group-terminated urethane prepolymer is not particularly limited, and for example, in the presence of the above-mentioned active hydrogen-containing compound (A) and polyisocyanate (B), and the additive (C) described later. Examples thereof include a method of making a urethanization reaction. Therefore, the curable resin composition containing the obtained NCO group-terminated urethane prepolymer may contain the additive (C).

The reaction temperature when synthesizing the urethane prepolymer is not particularly limited, but is preferably in the range of 50 ° C. to 130 ° C.

<Fillers and additives>
The curable resin composition used in the present invention contains one or more selected from the group consisting of the filler (C) and the additive (D).

The filler (C) is not particularly limited, and for example, any filler such as an inorganic filler, an organic filler, and a fibrous filler can be selected and used.

Specifically, silica such as fumed silica, precipitated silica, crystalline silica, molten silica, dolomite, silicic anhydride, hydrous silicic acid, fatty acid-treated calcium carbonate, heavy calcium carbonate, and calcium carbonate such as collagen carbonate. , Carbon black, magnesium carbonate, magnesium hydroxide, iron oxide, zinc oxide, silica soil, calcined clay, clay, talc, titanium oxide, barium sulfate, kaolin, zeolite, bentonite, organic bentonite, aluminum, flint powder and other pigments, Examples thereof include silas balloon, glass microballoon, phenol resin / vinylidene chloride resin, polyvinyl chloride / polymethyl methacrylate, synthetic resin powder such as polystyrene, asbestos, glass fiber, and glass filament. Such a filler may be used alone or in admixture of two or more, and may be surface-treated with an appropriate surface treatment agent.

Among these, an inorganic filler is preferable from the viewpoint of stainability, elasticity, and durability of the obtained cured product, and specifically, fumed silica, precipitated silica, crystalline silica, and molten silica. Silica such as dolomite, silicic acid anhydride, hydrous silicic acid, calcium carbonate such as fatty acid-treated calcium carbonate, heavy calcium carbonate, and collagen carbonate, carbon black, magnesium carbonate, magnesium hydroxide, iron oxide, zinc oxide, silica soil, Pigments such as calcined clay, clay, talc, titanium oxide, barium sulfate, kaolin, zeolite, bentonite, organic bentonite, aluminum and flint powder are exemplified as suitable inorganic fillers.

The content of the filler when used is not particularly limited, but is preferably in the range of 0.1 to 80% by weight, more preferably 20 to 80% by weight in the curable resin composition from the viewpoint of physical characteristics of the cured material. It is in the range of% by weight.

Examples of the additive (D) include a urethanization catalyst, a light stabilizer, an antioxidant, a plasticizer, a solvent, a leveling material, a thixotropy agent, a foam stabilizer, an antifoaming agent, a flame retardant, a foaming agent, and a release agent. Examples include molds, latent hardeners, antistatic agents, silane coupling agents and the like. It is preferable to contain any one or more of these additives, and more preferably two or more of these additives are contained.

The additive (D) is appropriately selected depending on the intended use and required physical characteristics. For example, a light stabilizer and an antioxidant are preferably used because they can easily maintain long-term stain resistance of the cured product.

The antioxidant is not particularly limited, and examples thereof include compounds having an effect of suppressing oxidation of polymer chains such as thioether compounds, phosphorus antioxidants, and hindered phenol compounds, and the trade name is Ciba. Irganox manufactured by the company and Adecastab manufactured by Adeca.

Among them, a hindered phenol-based antioxidant is preferable as the antioxidant, and since it is easy to obtain antioxidant properties against urethane, 2,6-di-t-butyl-4-methylphenol (BHT), Ciba Japan It is particularly preferable to use one or more antioxidants selected from IRGANOX-1010, IRGANOX-1024, IRGANOX-1035, IRGANOX-1076, and IRGANOX-1081.

The light stabilizer is not particularly limited, but for example, a benzotriazole-based compound, a triazine-based light stabilizer, a benzophenone-based light stabilizer, an ultraviolet absorber such as a benzoate-based compound, a hindered amine-based light stabilizer, etc. Examples of compounds have the effect of imparting sex, etc., and the trade name is tinubin manufactured by Ciba Japan.

Among them, as the light stabilizer, it is preferable to use one or more selected from chinubin 234, chinubin 144, chinubin C353, and chinubin B75. These antioxidants and light stabilizers can also be mixed and used.

Further, a urethanization catalyst is preferably used because it exhibits high curability and tends to improve workability.

Examples of the urethanization catalyst include organic tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and tin 2-ethylhexanoate, iron compounds such as iron acetylacetonate and iron chloride, and lead octylate. Examples thereof include lead compounds, bismuth compounds such as bismuth octylate, and tertiary amine-based catalysts such as triethylamine and triethylenediamine, and one or more catalysts selected from organotin compounds, lead octylate, and bismuth octylate are preferable. ..

In addition, a plasticizer is preferably used in order to develop flexibility and enhance the followability to the substrate.

The plasticizer is not particularly limited, and for example, phthalates, non-aromatic dibasic acid esters, aliphatic esters, polyalkylene glycol esters, phosphoric acid esters, trimellitic acid esters, etc. Examples thereof include chlorinated paraffins, hydrocarbon oils, process oils, polyethers, epoxy plasticizers, polyester plasticizers and the like, and phthalates are preferable. Specifically, dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, dioctyl phthalate, dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate, tricresyl phosphate, tributyl phosphate, epoxidized soybean oil. , Benzyl epoxy stearate and the like.

Such plasticizers can be used alone or in admixture of two or more, or may be added during the production of the urethane prepolymer.

In addition, a solvent is preferably used because the viscosity is lowered and the workability is improved.

As a solvent, it is used for the purpose of diluting to lower the viscosity of the curable resin composition and improving workability. For example, acetone, methyl ethyl ketone, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, dipropyl ether. , N-hexane, n-heptane, toluene, xylene, cyclohexane, petroleum-based solvents such as mineral spirit and the like.

Of these, methyl ethyl ketone, ethyl acetate, toluene, mineral spirit and the like are preferable from the viewpoint of workability.

The foam stabilizer is not particularly limited, and examples thereof include silicone compounds. The defoaming agent is not particularly limited, and examples thereof include silicone compounds. The flame retardant is not particularly limited, and examples thereof include phosphorus compounds such as trischloropropyl phosphate and chlorine compounds. The release agent is not particularly limited, and examples thereof include silicone compounds. The latent curing agent is not particularly limited, and examples thereof include an aldimine compound, an oxime compound, ketimine, and oxazolidine. The thixotropy agent is not particularly limited, and examples thereof include urea derivatives such as fatty acid amide and BYK410.

When the additive (D) is used, the content thereof is not particularly limited, but preferably each component of the additive is in the range of 30% by weight or less of the curable resin composition of the present invention, and further. It is preferably in the range of 15% by weight or less, and most preferably in the range of 0.5% by weight or less. When a urethanization reaction catalyst is used, it is preferably used in the range of 0.0001 to 1% by weight, more preferably 0.001 to 0.1% by weight of the curable resin composition.

Further, the curable resin composition of the present invention may contain an isocyanate compound other than the NCO group-terminated urethane prepolymer as long as the purpose is not impaired, and preferably less than 30% by weight in the curable resin composition. It is in the range of, and more preferably not included.

<Curable resin composition>
The curable resin composition used in the present invention is preferably in the form of a liquid or a paste.

In the curable resin composition used in the present invention, the active hydrogen-containing compound (A) and the polyisocyanate (B) are prepolymerized at an arbitrary timing, and the filler (C) and the additive (D) are formed at an arbitrary timing. Can be mixed and manufactured. For example, in addition to the prepolymer method for preparing a curable resin composition by mixing and prepolymerizing the active hydrogen-containing compound (A) and the polyisocyanate (B), the active hydrogen-containing compound (A), and the polyisocyanate (B). Further, a one-shot method in which a curing agent is mixed to prepare a curable resin composition in the system and the curing is performed can be mentioned, but the prepolymer method is preferable from the viewpoint of workability and stability of physical properties.

Specifically, the active hydrogen-containing compound (A), the polyisocyanate (B), and if necessary, the additive (D) are prepolymerized in the presence of a urethanization catalyst, and further, the filler (C) and the additive (D) are formed. ) To prepare a curable resin composition, the active hydrogen-containing compound (A) and the polyisocyanate (B) are reacted in the presence of the filler (C) and the additive (D) to form an NCO group. A method for preparing a curable resin composition containing a terminal urethane prepolymer, an active hydrogen-containing compound (A) and a polyisocyanate (B) are mixed, and a filler (C) and an additive (D) are mixed during the prepolymerization. ) Is added to allow the reaction to proceed. The order and method of adding these are arbitrary and are not particularly limited. The additive (C) may be used as a masterbatch.

The active hydrogen-containing compound (A), filler (C), and additive (D) used in the curable resin composition are preferably dehydrated by vacuum heating or the like, but are dehydrated in terms of workability and curability. You may use it without it.

As a method for preparing the curable resin composition, for example, various dispersion methods that are uniformly dispersed can be used. As the stirrer, a general-purpose stirrer, a dispenser disperser, a dissolver, a kneader, a mixer, a lab plast mill, a planetary mixer, etc. can be used, and when a filler is used, the mixture is mixed with a kneader, a mixer, a lab plast mill, a planetary mixer, etc. Is preferable. Stirring and mixing may be carried out under nitrogen, or while heating or defoaming under reduced pressure, if necessary.

The above-mentioned curable resin composition can be suitably used as a coating material composition from the viewpoint of workability and foam resistance.

<Coating material composition>
The above-mentioned curable resin composition can form a coating material composed of one liquid of the curable resin composition or two or more liquids with a curing agent by reacting with various active hydrogen-containing compounds.

The one-component type includes a one-component moisture-curing type that cures by reacting with moisture in the air, and a one-component latent curing agent type that cures with an active hydrogen-containing compound obtained from a latent curing agent (1.5-component type). (Sometimes referred to as), etc.), etc., and for two or more liquids, a two-component curing type in which the main agent containing the curable resin of the present invention is mixed with a curing agent and other auxiliary materials to be cured can be mentioned. It can be selected and used according to its characteristics.

The coating material composition of the present invention is preferably a two-component type because it is easy to handle and is easy to work with various waterproof materials such as spraying.

Here, examples of the active hydrogen-containing compound include the above-mentioned moisture in the air, a curing agent, a deprotected body of a latent curing agent, and the like.

The curing agent may contain at least one compound having one or more active hydrogen groups, and is not particularly limited. For example, water, polypropylene glycol, polyethylene propylene glycol, ethylene glycol (EG), diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol (1,4-BD), 1, Diols such as 6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and 1,4-dihydroxycyclohexane, polypropylene triol, polyethylene propylene triol, glycerin, trimethylolpropane (TMP), triethanolamine, etc. Modified with triols, polypropylene tetraol, polyethylene propylene glycol, castor oil, shoecrose, tetrafunctional or higher functional polyols such as sorbitol, 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA), aniline, etc. Modified polyamines such as modified MOCA, aromatic amines such as toluenediamine, diphenylmethanediamine, diethyltoludiamine, aliphatic amines such as ethylenediamine, polyamines such as Jeffamine ED, aminoalcohols such as ethanolamine and diethanolamine, and two of these. Examples include a mixture of more than seeds. Examples of the curing agent combination system include a MOCA-polyester combination curing agent in which an aromatic amine is mixed with polyalkylene oxide.

Among them, polyalkylene oxides such as polypropylene polyols and polyethylene propylene polyols are easy to develop sufficient curability and appropriate pot life, and easily develop mechanical properties and durability of the obtained urethane cured product. , 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA), modified polyamines such as modified MOCA modified with aniline, MOCA modified with tolylenediisocyanate, metaxylylenediamine, toluenediamine, MOCA-polyol. It is preferably at least one selected from the group consisting of the combined curing agent.

When producing a two-component curing type coating material composition, by using it as a curing agent solution in which a filler (C) and an additive (D) are added to the above curing agent, the volume ratio of the main agent to the curing agent solution is 1 : It is easy to control in the range of 0.2 to 3, and since work mistakes are reduced, workability is improved, and composition variation is reduced, it becomes easy to obtain a low-contamination two-component curable coating material composition.

When a polyalkylene oxide such as polypropylene polyol or polyethylene propylene polyol is used as the curing agent, the degree of unsaturation of the polyalkylene oxide is 0.010 meq / because it is easy to obtain a urethane resin having remarkably good stain resistance, although it is not particularly limited. It is preferably a 2- to 4-functional polyalkylene oxide synthesized by using a base catalyst and a Lewis acid catalyst in combination, having a molecular weight in the range of 500 to 10000 and a molecular weight distribution of 1.039 or less in g or less.

If necessary, the curing agent may include a wetting dispersant, a solvent, a leveling material, an antioxidant, an antioxidant, a light stabilizer, a filler, and a plasticizer.

The amount of the curing agent added is in the range in which the equivalent ratio (NCO / RH) of the NCO group contained in the main agent containing the curable resin composition to the active hydrogen group contained in the curing agent is 0.7 to 2.0. It is preferable to add with. More preferably, it is added in a range where NCO / RH is 1.0 to 1.5. The amount of the curing agent added is preferably in the range of 20 to 300 parts by weight with respect to 100 parts of the main agent containing the curable resin composition because the workability is easily excellent.

Using the coating material composition of the present invention, a coating film, a film sheet, or a thick material of any thickness can be applied by hand coating or mechanical coating such as coating with a spatula, comb, roller, iron, rake, etc. Etc. can be any shape. It is also possible to blend a compound having a sagging property and coat an elevation, a wall surface, a surface, a depression or the like with a roller, a ricin gun, an airless gun or the like to form a coating film or a cured product.

The coating material composition of the present invention can be made into a thick shape because it is easily cured, and a low-thickness shape and a wide range of shapes because it is excellent in physical characteristics. For example, since it can be cured from a low thickness to a high thickness regardless of the presence or absence of a curing agent, it can be preferably used when the shape has a thickness of 10 mm or less, and particularly preferably when the shape has a thickness of 5 mm or less. it can. It may be further thickened after being slightly cured. When used as a floor material / waterproofing material for a coating film, the thickness is preferably 1 to 10 mm, more preferably 2 to 4 mm.

<Coating material>
The coating material, which is a cured product of the coating material composition of the present invention, has a feature of excellent stain resistance, and any one-component moisture-curing type, two-component curing type, or 1.5-component type can be preferably used. It is preferably a two-component curing type using an aromatic amine-based curing agent and / or a curing agent such as polyalkylene oxide.

The coating material of the present invention can be suitably used for flooring materials and waterproof materials from the viewpoint of stain resistance, but is not particularly limited. Flooring materials and waterproofing materials include coating film waterproofing materials for balconies and rooftops of buildings, waterproof sheets, coating film waterproofing materials for vehicles, flooring materials for apartments, detached houses, hospitals, etc., elastic paving materials for sports facilities, etc. , Anti-rust material such as metal and the like.

The coating material of the present invention is preferably composed of a single layer or a plurality of layers containing at least one layer (cured urethane layer) containing the coating material of the present invention. For example, a single-layer structure containing only a urethane cured product layer, a urethane cured product layer, a two-layer structure of a top coat layer, a three-layer structure of two urethane cured product layers and a top coat layer, a urethane cured product layer, a reinforcing material layer or ventilation. Examples thereof include a four-layer structure of a sheet, a urethane cured product layer, and a top coat layer.

As a method of applying the coating material of the present invention, for example, at the construction site, a main agent solution containing a curable resin composition, a curing agent solution, and if necessary, other additive solutions are mixed with a mixing mixer, and it is necessary. It is obtained by applying a primer-treated substrate to a thickness of about 1 to 4 mm and curing the substrate, and it is preferable to apply a top coat on the coating film. Examples of the coating method include hand coating and spraying, which can be preferably used.

Where a high thickness is required, it is possible to recoat the cured product or the reinforcing material layer, which has been cured to some extent, to a thickness of about 1 to 4 mm to cure the material.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention will not be construed as being limited to the following Examples as long as the gist of the present invention is not exceeded. The raw materials used in the following Examples and Comparative Examples and the evaluation method are as shown below.

(material)
<Polyprethane>
The properties of the polyol used in Examples or Comparative Examples are also shown in Tables 1 and 2.

Polyols (A1) to (A3): Sufficient dehydration and desolvation in combination with an imino group-containing phosphazenium salt (IPZ) catalyst and triisopropoxyaluminum, and sufficient for polyoxypropylene glycol having a bifunctional molecular weight of 400. Bifunctional polyalkylene oxide to which dehydrated propylene oxide is added.

Polyol (A4): Commercially available general-purpose polyoxypropylene glycol (PP-2000 manufactured by Sanyo Chemical Industries, Ltd.).

Polyol (A5): Commercially available general-purpose polyoxypropylene glycol (PP-4000 manufactured by Sanyo Chemical Industries, Ltd.).

Polyesters (A6), (A7): Polyalkylene oxide obtained by adding propylene oxide to polyoxypropylene glycol having a bifunctional molecular weight of 400 using a composite metal cyanide complex (DMC) catalyst.

Polyols (A8), (A9): Sufficient dehydration and desolvation in combination with imino group-containing phosphazenium salt (IPZ) catalyst and triisopropoxyaluminum, sufficient for polyoxypropylene triol with trifunctional molecular weight of 400 trifunctional polyalkylene oxide obtained by adding dehydrated propylene oxide.

Polyol (A10): A trifunctional polyalkylene oxide obtained by adding propylene oxide to a polyoxypropylene polyol having a trifunctional molecular weight of 400 by a conventional method using only an imino group-containing phosphazenium salt (IPZ) catalyst.

Polypoly (A11): Commercially available general-purpose trifunctional polyoxypropylene polyol (GP-4000 manufactured by Sanyo Chemical Industries, Ltd.).

Polyester (A12): Polyalkylene oxide polyol (A13) in which propylene oxide is added to polyoxypropylene glycol having a trifunctional molecular weight of 1000 using a composite metal cyanide complex (DMC) catalyst: Commercially available polytetramethylene glycol (Mitsubishi Chemical). PTMG2000 manufactured by the company).

The above polyol was heated and vacuum dehydrated before use. Except for commercially available products, the catalyst was removed and used by a conventional method.

The polyol (A3) had a narrow degree of unsaturation and a narrow molecular weight distribution, and had a lower viscosity than the polyol (A7).

The polyols (A1), (A2), (A8), and (A9) had a narrow degree of unsaturation and a narrow molecular weight distribution. On the other hand, the polyols (A4), (A5), (A10), and (A11) had a high degree of unsaturation.

<Polyisocyanate>
Polyisocyanate (C1): Tolylene diisocyanate (mixture of 2,4-TDI 80% and 2,6-TDI 20%, Coronate T-80 manufactured by Tosoh Corporation).

Polyisocyanate (C2): Polymethylene polyphenylene polyisocyanate (Polymeric MDI) (Millionate MR-200 manufactured by Tosoh Corporation, NCO content 31.5% by weight).

These were used as they were without purification.

<Filler>
Filler (D1): Heavy calcium carbonate (Whiten SB manufactured by Maruo Calcium Co., Ltd.).

Filler (D2): Titanium oxide (Typake R820 manufactured by Ishihara Sangyo Co., Ltd.).

The above commercial product was heated and vacuum dehydrated before use.

<Additives>
Additive (E1): Hindered phenolic antioxidant (BASF's Irganox 1010)
Additive (E2): Bismuth octylate (Pucat 25 manufactured by Nihon Kagaku Sangyo Co., Ltd.)
Additive (E3): Dioctyl phthalate (DOP manufactured by Daihachi Chemical Co., Ltd.)
The above-mentioned commercial product was used as it was.

<Hardener>
Hardener (F1): 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA) (Ihara Chemical Industry Co., Ltd., Ihara Curemine MT).

Hardener (F2): The polyol (A1) (molecular weight 2000).

As the curing agent (F1), a commercially available product was used as it was. The curing agent (F2) was heated and vacuum dehydrated before use.

(Evaluation method of curable resin composition)
<Hydroxy group value, number average molecular weight>
The hydroxyl value (OHV) of the polyalkylene oxide was measured according to the method of JIS-K1557-1. The number average molecular weight of the polyalkylene oxide is a value calculated using the above formula (4) based on the hydroxyl value of the polyalkylene oxide.

<Degree of unsaturation>
The measurement was performed according to the method of JIS-K1557-6.

<Molecular weight distribution (Mw / Mn)>
10 mg of polyol and 10 ml of THF were added to the sample bottle, dissolved by allowing to stand overnight, and filtered through a PTFE cartridge filter (0.5 μm) to obtain a sample. The RI detector RI8020 is connected in series as the detector, and a total of four Tskgel SuperH4000 x 2 and Tskgel SuperH3000 x 2 manufactured by Tosoh, whose separation column is filled with a filler having a particle size of 3 μm, are connected in series, and the reference side is a resistance tube. × 5 are connected, special grade tetrahydrofuran containing BHT stabilizer manufactured by Wako Co., Ltd. is used as the developing solvent, and the flow rate on the separation column side is 0.6 ml / min, the flow rate on the reference side is 0.15 ml / min, and the column temperature is 40 ° C. analyzed. The molecular weight distribution (Mw / Mn) was analyzed using a third-order approximation curve using eight standard polystyrenes manufactured by Tosoh Corporation with a known molecular weight as a calibration curve. Tosoh's HLC-8320GPC was used as the measuring device, and Tosoh's HLC-8320GPC-ECOSEC-Workstation was used for the analysis.

<Measurement of free isocyanate content>
The content of free isocyanate remaining in the main agent was measured according to JIS K7301-6-4.

When 0.5% by weight or more of the free polyisocyanate monomer having a molecular weight of 200 or less, which causes bleeding, remains in the curable resin composition, it is judged to be a highly contaminated composition. In addition, it can be judged that the work environment is bad and the workability is poor.

<Workability>
The workability of the curable resin composition as a coating film waterproof material was evaluated as follows.

◯: Can be applied and stretched with a spatula or iron at room temperature ×: Too viscous and difficult to install Note that the evaluation is casting when creating a urethane cured product and stretching with a spatula. Judged by operation.

<Curable>
The time required for curing the curable resin composition coated to a thickness of about 2 mm was evaluated as follows. The curable resin composition being cured was touched with a finger over time, and the time during which the tack disappeared was used as an index of the time during which walking was possible using the floor material. If it is less than 3 hours, it is judged that the curability is inferior XX (failed) because the workable period is short and the curing time required for the work cannot be taken.

◯: When it takes 3 hours or more and less than 6 hours △: When it takes 6 hours or more and less than 12 hours ×: When it takes 12 hours or more XX: When it takes less than 3 hours (curing progresses too early and the pot life is short)
<Effervescent>
The appearance of the cured product when the curable resin composition was cured with a metal mold having a thickness of about 2 mm was visually evaluated.

◯: Visually uniform surface appearance Δ: Bubbles remain on a part of the surface of the cured product ×: Bubbles remain on one surface of the cured product <Contaminability of base material>
The curable resin composition was cured and peeled off after 2 weeks, and the stainability on the metal mold was evaluated as an index of the stainability of the base material. Silica sand No. 7 was sprayed on a metal mold and allowed to stand for 1 minute, and the state of deposits remaining even when turned upside down was observed. The evaluation criteria were as follows.

◯: No adhesion of silica sand (less than 5% of surface area)
Δ: Slight adhesion of silica sand was observed and can be removed by tapping (remaining less than 5% of the surface area).
X: Adhesion of silica sand is observed and remains on the surface even when hit (remaining 5% or more of the surface area)
Regarding the contaminating property of the base material, ○ was passed, △, and × were rejected, and those that did not pass were judged to be difficult to use as flooring materials and waterproof materials because there is a risk of contaminating the surroundings when constructed.

<Manufacturing of curable resin composition and its cured product>
The properties of the urethane prepolymer used in Examples or Comparative Examples are also shown in Tables 3 and 4.

Example 1.
A low-saturation, narrow-molecular-weight distribution polyol (A1) and a polyol (A8) were placed in a four-port separable flask equipped with a stirring blade so as to have a weight ratio of 55:45, and at 100 ° C. for 2 hours. Dehydration under reduced pressure was performed. After cooling to room temperature, TDI (Tosoh Coronate T-80) is prepared under nitrogen so that the ratio of TDI to polyol (A2) and polyol (B1) is 1.9 in terms of NCO / OH ratio. The mixture was placed in a bull flask and stirred under nitrogen at 80 ° C. without catalyst until the consumption of NCO groups stopped, to synthesize an NCO group-terminated urethane prepolymer.

Irganox 1010 as an antioxidant and dioctyl phthalate as a plasticizer were added to the obtained NCO group-terminated urethane prepolymer and stirred to prepare a liquid composition, which was used as the main component of the curable resin composition. The amount of free TDI in the main agent was small, and the work environment and workability were excellent.

Further, heavy calcium carbonate as a filler, bismuth octylate as a catalyst, dioctyl phthalate as a plasticizer, and MOCA as a curing agent are mixed under nitrogen to prepare a liquid composition, which is used as a curing agent for a curable resin composition. did. The two liquids of the main agent and the curing agent of the curable resin composition were kneaded with a kneader under nitrogen at 50 ° C. to obtain a paste-like curable resin composition. The ratio of the main agent to the curing agent was about 1: 1 and the workability was excellent.

Next, the obtained curable resin composition was poured into a metal mold having a thickness of 2 mm from which a release agent was applied and excess was removed, defoamed, and then coated and stretched with a spatula so as to have a thickness of 2 mm. A urethane cured product was obtained by allowing it to stand at 23 ° C. and 50% RH and curing.

The obtained curable resin composition had a low viscosity, was easy to put into a mold, and was easy to apply and stretch, and was excellent in workability.

In addition, the obtained curable resin composition does not show foaming as the curing progresses and has excellent foaming resistance. Since the time required for curing is short, it has excellent curability, and can be used for flooring materials, waterproof materials for coating films, etc. Was expected to be applied.

The obtained cured urethane product did not bleed or contaminate the metal mold even when peeled off, and was excellent in stain resistance to the surroundings.

Example 2.
A main agent of a liquid curable resin composition was prepared by the same method as in Example 1 except that dioctyl phthalate was removed as an additive.

Further, titanium oxide was added to the filler to change the composition of the filler, dioctylphthalate was removed as an additive, and MOCA-PPG was used as a curing agent to increase the amount of the catalyst, and the amount of the catalyst was increased by the same method as in Example 1. A curable resin composition and a urethane cured product were obtained.

The curable resin composition has a low viscosity, is easy to put into a mold, and is easy to apply and stretch, and has excellent workability. The ratio of the main agent to the curing agent was about 1: 1 and the workability was excellent.

In addition, the obtained curable resin composition does not show foaming as the curing progresses and has excellent foaming resistance. Since the time required for curing is short, it has excellent curability, and can be used for flooring materials, waterproof materials for coating films, etc. Was expected to be applied.

The obtained cured urethane product did not bleed or contaminate the metal mold even when peeled off, and was excellent in stain resistance to the surroundings.

Example 3.
A paste-like curable resin composition and a urethane cured product were obtained by the same method as in Example 2 except that the composition ratio of the filler was changed and the amount of the catalyst was increased by using only the polyol (A1) as the curing agent. .. The curable resin composition has a low viscosity, is easy to put into a mold, and is easy to apply and stretch, and has excellent workability. The ratio of the main agent to the curing agent was about 1: 2, and the workability was excellent.

In addition, the obtained curable resin composition does not show foaming as the curing progresses and has excellent foaming resistance. Since the time required for curing is short, it has excellent curability, and can be used for flooring materials, waterproof materials for coating films, etc. Was expected to be applied.

The obtained cured urethane product did not bleed or contaminate the metal mold even when peeled off, and was excellent in stain resistance to the surroundings.

Example 4.
A main agent of the curable resin composition was prepared by the same method as in Example 1 except that the polyol (A2) was used instead of the polyol (A1), and a curable resin composition and a urethane cured product were obtained.

The main agent of the obtained curable resin composition had a small amount of free TDI and was excellent in working environment and workability.

The obtained curable resin composition has a low viscosity, is easy to put into a mold, and is easy to apply and stretch, and has excellent workability. The ratio of the main agent to the curing agent was about 1: 1 and the workability was excellent.

In addition, the obtained curable resin composition does not show foaming as the curing progresses and has excellent foaming resistance. Since the time required for curing is short, it has excellent curability, and can be used for flooring materials, waterproof materials for coating films, etc. Was expected to be applied.

The obtained cured urethane product did not bleed or contaminate the metal mold even when peeled off, and was excellent in stain resistance to the surroundings.

Example 5.
A polyol (A2) was used instead of the polyol (A1), and the main agent of the curable resin composition was prepared by the same method as in Example 3 except that the filler was removed, and the curable resin composition and the urethane cured product were prepared. Got

The main agent of the obtained curable resin composition had a small amount of free TDI and was excellent in working environment and workability.

The obtained curable resin composition has a low viscosity, is easy to put into a mold, and is easy to apply and stretch, and has excellent workability. The ratio of the main agent to the curing agent was about 1: 1 and the workability was excellent.

Further, since the obtained curable resin composition does not contain a filler, foaming accompanying the progress of curing is slightly observed on the surface as compared with Example 3, but the foaming resistance is excellent. .. Since the time required for curing is short, it has excellent curability and can be expected to be applied to flooring materials, waterproof coating materials, and the like.

The obtained cured urethane product did not bleed or contaminate the metal mold even when peeled off, and was excellent in stain resistance to the surroundings.

Example 6.
The same method as in Example 2 except that the polyol (A2) was used instead of the polyol (A1), the ratio of the polyol (A2) to the polyol (A8) was changed to 70:30, and the composition ratio of the filler was adjusted. The main agent of the curable resin composition was prepared, and a curable resin composition and a urethane cured product were obtained.

The main agent of the obtained curable resin composition had a small amount of free TDI and was excellent in working environment and workability.

The obtained curable resin composition has a low viscosity, is easy to put into a mold, and is easy to apply and stretch, and has excellent workability. The ratio of the main agent to the curing agent was about 1: 1 and the workability was excellent.

In addition, the obtained curable resin composition does not show foaming as the curing progresses and has excellent foaming resistance. Since the time required for curing is short, it has excellent curability, and can be used for flooring materials, waterproof materials for coating films, etc. Was expected to be applied.
The obtained cured urethane product did not bleed or contaminate the metal mold even when peeled off, and was excellent in stain resistance to the surroundings.

Example 7.
The same method as in Example 2 except that the polyisocyanate was changed from TDI to polyfunctional polymeric MDI, the NCO / OH ratio during prepolymer synthesis was changed from 1.9 to 2.4, and the amount of filler was adjusted. To prepare a main agent of the curable resin composition, a curable resin composition and a urethane cured product were obtained.

The obtained curable resin composition has a low viscosity, is easy to put into a mold, and is easy to apply and stretch, and has excellent workability. The ratio of the main agent to the curing agent was about 1: 1 and the workability was excellent.

In addition, the obtained curable resin composition does not show foaming as the curing progresses and has excellent foaming resistance. Since the time required for curing is short, it has excellent curability, and can be used for flooring materials, waterproof materials for coating films, etc. Was expected to be applied.

The obtained cured urethane product did not bleed or contaminate the metal mold even when peeled off, and was excellent in stain resistance to the surroundings.

Example 8.
Curability by the same method as in Example 2 except that the polyol (A3) and the polyol (A9) were used in the ratio of 40:60 instead of the polyol (A1) and the polyol (A8) and the composition ratio of the filler was adjusted. The main agent of the resin composition was prepared, and a curable resin composition and a urethane cured product were obtained.

The main agent of the obtained curable resin composition had a small amount of free TDI and was excellent in working environment and workability.

The curable resin composition has a low viscosity, is easy to put into a mold, and is easy to apply and stretch, and has excellent workability. The ratio of the main agent to the curing agent was about 1: 1 and the workability was excellent.

In addition, the obtained curable resin composition does not show foaming as the curing progresses and has excellent foaming resistance. Since the time required for curing is short, it has excellent curability, and can be used for flooring materials, waterproof materials for coating films, etc. Was expected to be applied.

The obtained cured urethane product did not bleed or contaminate the metal mold even when peeled off, and was excellent in stain resistance to the surroundings.

Example 9.
A polyol (A4) was used instead of the polyol (A3), the ratio of the polyol (A4) to the polyol (A9) was set to 10:90, and the curing was performed by the same method as in Example 8 except that the composition ratio of the filler was adjusted. The main agent of the sex resin composition was prepared, and a curable resin composition and a urethane cured product were obtained. Since the degree of unsaturation of the polyol (A4) is high, a small amount (10 parts) was used.

The main agent of the obtained curable resin composition had a small amount of free TDI and was excellent in working environment and workability.

The obtained curable resin composition has a low viscosity, is easy to put into a mold, and is easy to apply and stretch, and has excellent workability. The ratio of the main agent to the curing agent was about 1: 1 and the workability was excellent.

Further, since the obtained curable resin composition contains a small amount of a polyol having a high degree of unsaturation, foaming with the progress of curing is slightly observed on the surface as compared with Example 8, but the foaming resistance is good. , It was expected to be applied to floor materials, waterproof coating materials, etc.

The obtained cured urethane product uses a polyol having a high degree of unsaturation, but in a small amount, there is no bleeding or contamination on the metal mold even when peeled off, and it is excellent in stain resistance to the surroundings. It was.

The above results are also shown in Table 5.

Comparative example 1.
Similar to Example 4 except that polyols (A5) and polyols (A11) having the same molecular weight and high degree of unsaturation were used instead of polyols (A2) and polyols (A8) having a low degree of unsaturation and a narrow molecular weight distribution. The main agent of the curable resin composition was prepared by the method, and the curable resin composition and the urethane cured product were obtained.

The main agent of the obtained curable resin composition had a large amount of free TDI and was inferior in working environment and workability.

Further, the obtained curable resin composition was inferior in curability because it had foaming as the curing progressed and the time required for curing was long.

Then, even when the obtained cured urethane product was peeled off, it was difficult to use it as a flooring material, a coating film waterproofing material, etc. because of strong bleeding and contamination on the metal mold and concern about contamination to the surroundings. ..

Comparative example 2.
Comparative example except that a polyol (A6) having a low degree of unsaturation but a wide molecular weight distribution and a polyol (A10) having a medium degree of unsaturation were used instead of the polyol (A5) and the polyol (A11) having a high degree of unsaturation. The main agent of the curable resin composition was prepared by the same method as in 1, and the curable resin composition and the urethane cured product were obtained.

The main agent of the obtained curable resin composition still contained free TDI, and was inferior in working environment and workability.

The obtained curable resin composition had foaming as the curing progressed, and was inferior in foaming resistance. Further, although the time required for curing was shorter than that of Comparative Example 1, it was inferior in curability because it was longer than that of Example 1.

Further, although the obtained cured urethane product is better than Comparative Example 1, bleeding and contamination of the metal mold when peeled off are still observed, and there is a concern of contamination to the surroundings. It was difficult to use as a coating film waterproofing material.

Comparative example 3.
The main agent of the curable resin composition was prepared by the same method as in Comparative Example 2 except that the polyol (A12) having a low degree of unsaturation but a wide molecular weight distribution was used instead of the polyol (A10) having a medium degree of unsaturation. A curable resin composition and a cured urethane product were obtained.

The main agent of the obtained curable resin composition still contained free TDI, which was inferior in working environment and workability.

The obtained curable resin composition had foaming as the curing progressed, and was inferior in foaming resistance. In addition, the time required for curing was still longer than that of the examples, and thus the curability was inferior.

The obtained cured urethane product is still bleeding and contaminated on the metal mold when peeled off, and there is a concern that it may contaminate the surroundings. Therefore, it can be used for flooring materials, waterproof materials for coating films, etc. It was difficult.

Comparative example 4.
The main agent of the curable resin composition was prepared by the same method as in Comparative Example 3 except that the MOCA curing system was changed to the PPG curing system and the amount of catalyst was increased except for the plasticizer and the filler, and the curable resin composition was prepared. A product and a cured urethane product were obtained.

The main agent of the obtained curable resin composition still contained free TDI, and was inferior in working environment and workability.

The obtained curable resin composition had foaming as the curing progressed, and was inferior in foaming resistance. In addition, the time required for curing was still longer than that of the examples, and thus the curability was inferior.

The obtained cured urethane product is still bleeding and contaminated on the metal mold when peeled off, and there is a concern that it may contaminate the surroundings. Therefore, it can be used for flooring materials, waterproof materials for coating films, etc. It was difficult.

Comparative example 5.
A curable resin composition was prepared by the same method as in Example 8 except that polyols (A7) and polyols (A12) having a low degree of unsaturation but a wide molecular weight distribution were used instead of the polyols (A3) and polyols (A9). The main agent of the above was prepared, and a curable resin composition and a urethane cured product were obtained.

The main agent of the obtained curable resin composition still contains free TDI, is inferior to the working environment, and uses a polyol having a wide molecular weight distribution and a low degree of unsaturation, so that it is extremely viscous and easy to handle. It was judged that it was difficult to install it as a flooring material or a waterproof material.

The obtained curable resin composition had foaming as the curing progressed, and was inferior in foaming resistance. In addition, the time required for curing was still longer than that of the examples, and thus the curability was inferior.

The obtained cured urethane product is still bleeding and contaminated on the metal mold when peeled off, and there is a concern that it may contaminate the surroundings. Therefore, it can be used for flooring materials, waterproof materials for coating films, etc. It was difficult.

Comparative example 6.
In order to improve the workability and foam resistance of the curable resin, the main agent of the curable resin composition was prepared by the same method as in Comparative Example 5 except that a plasticizer was added, and the curable resin composition and urethane were prepared. A cured product was obtained.

The main agent of the obtained curable resin composition had a viscosity within a range where construction was possible, but contained free TDI and was inferior to the working environment.

The obtained curable resin composition had foaming as the curing progressed, and was inferior in foaming resistance. In addition, the time required for curing was still longer than that of the examples, and thus the curability was inferior.

The obtained cured urethane product is still bleeding and contaminated on the metal mold when peeled off, and there is a concern that it may contaminate the surroundings. Therefore, it can be used for flooring materials, waterproof materials for coating films, etc. It was difficult.

Comparative example 7.
Using only the bifunctional polyol (A3), the main agent of the curable resin composition was prepared by the same method as in Example 5, and the curable resin composition and the urethane cured product were obtained.

The main agent of the obtained curable resin composition had a small amount of free TDI and was excellent in working environment and workability. However, since it was only a bifunctional polyol, it took time for the tack to disappear and the curability became curable. It was inferior.

The obtained cured urethane product is bleeding and contaminated on the metal mold when it is slightly peeled off, and there is a concern that it may contaminate the surroundings. Therefore, it can be used as a flooring material or a waterproof coating material. It was difficult.

Comparative example 8.
The ratio (NCO / OH) of the total amount of NCO groups contained in the polyisocyanate (C) to the total amount of OH groups contained in the active hydrogen-containing compound was changed from 1.9 to 1.3, and the curing agent was changed from MOCA-PPG to PPG alone. A main agent of the curable resin composition was prepared by the same method as in Example 8 except that the curable resin composition was obtained.

The main agent of the obtained curable resin composition had a small amount of free TDI and was excellent in a working environment, but it was very viscous, and the obtained curable resin composition was transferred to a mold. The operation and defoaming operation were difficult, it was difficult to obtain a uniform molded product, and subsequent evaluation was difficult.

Comparative example 9.
The curable resin composition and urethane were synthesized by the same method as in Example 6 except that the polyol (A13) (commercially available PTMG) was used instead of the polyol (A2) and the polyol (A8) and synthesized by the one-shot method. A cured product was obtained.

Since the obtained curable resin composition uses PTMG, it has a very viscous tone and is inferior in handleability, and it can be judged that it is difficult to construct it as a floor material or a waterproof material. In addition, the curing was too fast, the pot life was short, and the curing time required for the work could not be taken, and it was difficult to evaluate the contamination of the base material.

The above results are also shown in Table 6.

Example 10.
The curable resin composition prepared in Example 1 was stretched with a roller so as to have a thickness of 4 mm in a range of 1 m × 1 m, and allowed to stand for 12 hours to proceed with curing, and used as a coating film waterproof material. It could be easily applied as a coating material composition, and no unevenness due to foaming was observed even after curing. In addition, the obtained waterproof coating film showed good curability, was able to walk on it, and showed low contamination without contamination at the contact portion.

Claims (7)

One or two selected from the group consisting of an NCO group-terminated urethane prepolymer which is a reaction product of an active hydrogen-containing compound (A) and a polyisocyanate (B), a filler (C) and an additive (D). A curable resin composition containing the above.
The active hydrogen-containing compound (A) contains a bifunctional polyalkylene oxide (A1) and a trifunctional or higher functional polyalkylene oxide (A2 ) .
The more component of the bifunctional polyalkylene oxide (A1) and the trifunctional or higher functional polyalkylene oxide (A2) satisfies all of the following (a) to (d), and the NCO group-terminated urethane prepolymer is as follows. A coating material composition characterized by satisfying (e).
(A) The degree of unsaturation is 0.008 meq / g or less.
(B) The number average molecular weight calculated from the hydroxyl value (OHV) is 1000 to 15000 .
(C) The molecular weight distribution (Mw / Mn) determined by the (GPC) method by gel permeation chromatography using polystyrene as a standard substance is 1.003 to 1.039 .
(D) The molecular weight distribution (Mw / Mn) obtained by the gel permeation chromatography (GPC) method and the number average molecular weight (M) calculated from the hydroxyl value (OHV) satisfy the following mathematical formula (1).
(E) The ratio (NCO / OH) of the total amount of NCO groups contained in the polyisocyanate (B) to the total amount of OH groups contained in the active hydrogen-containing compound (A) is 1.5 to 3.0 (molar ratio). The polyisocyanate (B) is polymethylene polyphenylene polyisocyanate (Polymeric MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 1 , 5-Naphthalenediocyanate, trizine diisocyanate, xylylene diisocyanate, 1,4-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, these The composition according to claim 1, wherein the composition is at least one selected from the group consisting of the isocyanate-containing prepolymer of the above and the modified products of these isocyanates. Claim 1 or claim average functionality f _ave polyalkylene oxide (A1) and polyalkylene oxide (A2) and the combined polyalkylene oxide mixture, characterized in that in the range of 2.21 to 3.00 2. The composition according to 2. The composition according to any one of claims 1 to 3, wherein the filler (C) contains one or more inorganic fillers. Claims 1 to 4, wherein the additive (D) contains one or more selected from the group consisting of a urethanization catalyst, a light stabilizer, an antioxidant, a plasticizer, and a solvent. The composition according to any. The molecular weight distribution (Mw / Mn) of polyalkylene oxide obtained by gel permeation chromatography (GPC) using polystyrene as a standard substance is obtained by connecting four columns in series, each of which is a separation column filled with a filler having a particle size of 3 μm. The composition according to any one of claims 1 to 5, wherein a resistance tube is connected to the reference side, and the molecular weight distribution is analyzed under the condition that tetrahydrofuran is used as the developing solvent. A coating material comprising a cured product of the composition according to any one of claims 1 to 6.