JP2001278940A - Resin composition, decorative sheet using the same and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve such problem relating to a melamine formaldehyde resin that the melamine formaldehyde resin has been applied to a decorative sheet, coating material, molding material, etc., by utilizing whose excellent properties in harness, heat resistance, etc., with involving the problems that gas is evolved due to condensation at heat curing, it is hard to use for the applications required for acid resistance, etc. SOLUTION: The problem can be solved by using the resin composition comprising a aminotriazine compound, a (meth)acrylate prepolymer compound having a triazine ring synthesized form formaldehyde and a hydroxy(meth) acrylate, and an isocyanate compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a triazine ring-containing (meth) acrylate prepolymer resin composition, a decorative plate using the same, and a method for producing the same.

[0002]

2. Description of the Related Art Hitherto, resins having a triazine ring, for example, melamine formaldehyde resin, have been utilized in the fields of decorative boards, paints, molding materials and the like by making use of characteristics such as high hardness, heat resistance and insulation properties. However, since the obtained resin contains a solvent, a drying step is required, and there is a problem that a gas is generated due to the condensation reaction when heated and pressurized. In addition, it is particularly difficult to use it for special applications requiring acid resistance, such as a laboratory bench top plate. There are still insufficient points regarding the weather resistance, and problems such as being limited to indoor use have been addressed.

[0003]

The present invention can be molded in the absence of a solvent, and is particularly difficult to use in the field where chemical resistance is required. To solve the above problem.

[0004]

In the present invention, aminotriazine (hereinafter, referred to as AZ), formaldehyde, preferably paraformaldehyde (hereinafter, referred to as P) and hydroxyethyl (meth) acrylate (hereinafter, referred to as HA) are used.
A compound containing triazine ring-containing (meth) acrylate prepolymer (hereinafter referred to as TA) and an unreacted HA synthesized from a resin composition containing unreacted HA are reacted to form a solid that can be handled. The present invention has realized a decorative board in which the quality of the subject has been cleared by the manufacturing method of heating and pressing.

AZ is a compound having a structure in which an amino group is bonded to each of three carbon atoms of a triazine ring composed of carbon and nitrogen, and AZ indicates AZ itself or an AZ derivative. AZ itself includes melamine, and AZ derivatives include benzoguanamine, acetoguanamine, cyclohexanecarboguanamine, cyclohexanecarboguanamine, norbornenecarboguanamine, and the like.

P is a solid at room temperature, and is AZ in the present invention.
In addition, it can be used by dissolving it in hydroxy (meth) acrylate, and has an advantage that the steps of dehydration and desolvation are basically unnecessary as compared with the case of using a 37% aqueous solution of formaldehyde.

HA is an acrylate based 2-
Hydroxyethyl acrylate and 2-hydroxyethyl methacrylate based on ethyl methacrylate are included, and in the present invention, each of them can be used alone or in combination.

[0008] In addition to HA, at least one
Compounds having an ethylenically unsaturated bond having two hydroxyl groups, such as 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, trimethylpropanedi (meth) acrylate, Allyl alcohol, N-methylol (meth) acrylamide and the like or a mixture thereof can be used.

Synthesis of Prepolymer TA of the present invention is obtained by dehydration-condensation etherification by the reaction of a methylol group introduced by AZ and P with a hydroxyl group in HA, or methylol introduced by a reaction of P with HA. It is understood that the compound has been dehydrated, condensed and etherified by the reaction between the group and AZ.

In the synthesis of a prepolymer, AZ is used in HA.
If P and P are dissolved, the reaction can proceed. In some cases, a solvent such as alcohol or toluene may be blended in an appropriate amount for viscosity adjustment or the like, and the mixture may be reacted.

When melamine is used as the AZ and the reaction is carried out in the absence of a solvent, the molar ratio of melamine to P is preferably 1: 2 or more. The ratio is preferably at least 1: 2.

Although the prepolymer synthesis reaction can proceed without a catalyst, in order to promote the solubility and etherification reaction of AZ, an alkali such as sodium hydroxide, sodium carbonate, ammonia, and triethylamine may be added at first, During the reaction, an acid such as paratoluenesulfonic acid or hydrochloric acid which is an ether catalyst can be used.

Since this reaction proceeds in the presence of an ethylenically unsaturated bond, there is a concern of gelation due to addition polymerization. For this reason, it is necessary to add a quinone-based polymerization inhibitor or to introduce oxygen gas into the reaction system to advance the synthesis reaction. The reaction temperature is about 50 to 150 ° C., preferably about 70 to 130 ° C., and the reaction time is about 0.5 to 10 hours.

The thus synthesized TA has a (meth) acrylate group and an alkyl ether group on the triazine ring, and depending on the reaction conditions, a methylol group, an amino group,
It is a prepolymer containing HA. Although the average molecular weight varies depending on the blending and the reaction conditions, the average molecular weight is 200 to 80.
It is obtained as a prepolymer of about 00. Molecular weight 80
If it is more than 00, the viscosity becomes high, which is not preferable. If it is less than 200, the performance will be insufficient. Further, it is desirable that HA is left in an unreacted state to a necessary extent in order to promote the reaction with the isocyanate compound.

The isocyanate compound to be blended with the prepolymer includes, for example, isocyanate monomer, adduct, allophanate modified, buret modified, isocyanurate modified, carbodiimide, urethane prepolymer and the like. These can react with active hydrogen of a hydroxyl group, a methylol group, or an amino group contained in the TA, and the reaction yields a solid state in which the TA can be handled. By using the kind of these isocyanate compounds, for example, aliphatic isocyanate compound, a non-yellowing type compound and an aromatic compound having a yellowing type characteristic can be obtained.

A catalyst is not always required for the reaction with the isocyanate compound, but an amine-based or organometallic catalyst may be used in consideration of a curing method, workability, and the like.

The composition obtained according to the present invention has the above-mentioned TA
And an isocyanate compound as a main component, and a polymerization catalyst, a curing accelerator, and the like are added thereto, and if necessary, a filler, an ultraviolet absorber, a coloring agent, and the like are added and used.

As the polymerization catalyst, for example, organic peroxides, azo compounds and the like are used.

The thus-prepared composition is formed into a sheet by adding a coat or impregnation or a fiber chop to a base material such as nonwoven fabric, matte or the like processed from paper, synthetic fiber, glass fiber, etc. A prepreg sheet that can be handled is obtained by reacting a hydroxyl group or a methylol group, an amino group and an isocyanate group therein.

These prepreg sheets are singly or plurally stacked and hot-press molded to flow the resin, and the unsaturated groups in the TA are polymerized to obtain a molded plate.

[0021]

EXAMPLE In a separable flask equipped with a stirrer, a thermometer and a gas injection tube, 781 parts (6 mol) of 2-hydroxymethacrylate, 126 (1 mol) of melamine, 95
% P189g (6 mol) was added and the temperature was raised. After melamine and P 2 are dissolved in 2-hydroxymethacrylate, 3.0 g of paratoluenesulfonic acid is added, the internal temperature is maintained at 90 to 120 ° C., and the mixture is reacted while blowing air therein, and contains unreacted 2-hydroxymethacrylate. Reacted until the amount was 40%. The obtained TA having a hydroxyl group and a polymerizable unsaturated bond has a viscosity at 20 ° C of 1000.
mPa · sec and bromine value was 92.1. Using the TA obtained above, a curable composition was obtained according to the formulation shown in Table 1.

[0022]

[Table 1] * 1 Isocyanate compound Hexamethylene diisocyanate * 2 Curing agent 50% t-hexylperoxy 2-ethyl hexanoate (dioctyl phthalate dilution) * 3 Accelerator dibutyltin dilaurate * 4 Filler Average particle diameter 7 microns Methacrylsilane surface treated silica

[0023]

Example 1 A composition formulated according to A in Table 1 was mixed with 60
g / m2, applied to a glass nonwoven fabric having a density of 0.13 / cm3 so as to have a concentration of 300 g / m2, and react a hydroxyl group and an isocyanate group in the composition at room temperature to form a solid that can be handled. A prepreg sheet of Example 1 was obtained.

[0024]

Example 2 A composition formulated according to B in Table 1 was mixed with 60
g / m2, density 0.13g / m3 After coating so that the weight becomes 600g / m2, the hydroxyl group and the isocyanate group in the composition are reacted at room temperature to be a solid state that can be handled. The prepreg sheet of Example 2 was obtained.

Comparative Example 2.0 mol of formaldehyde per mol of melamine
After adding 37 mol of formalin, adjusting the pH to 9.0 with caustic soda, heating and dissolving the mixture and reacting with methylol, the mixture was aged at 80 ° C and concentrated to obtain a water-soluble melamine resin having a solid content of 60%. Was. Then, 0.5 parts by weight of paratoluenesulfonic acid as a curing accelerator was added thereto, and
g / m2 titanium paper impregnated to 300 g / m2,
It was dried to obtain a melamine / formaldehyde resin impregnated paper. Each of these impregnated papers is stacked on each sheet in the table at 150 ° C.
It was molded at g / cm2 to obtain a melamine resin laminate.

Formed sheets were prepared by laminating the prepreg sheets of Examples 1 and 2 and Comparative Example at a temperature of 100 ° C. and 20 kg / cm 2, each of which is shown in the table. The performance of each molded plate was as shown in the table. The performance of the molded plate according to the example was as shown in Table 2.

[0027]

[Table 2]

Test Method * 1 Acid resistant 35% hydrochloric acid was dropped on the surface of the molded plate, and after 24 hours, the surface was washed with water and judged by the presence or absence of abnormality. * 2 Heat resistance According to JIS K6902 (Testing method for thermosetting resin decorative board). * 3 Cigarette resistance test Appearance evaluation after igniting a cigarette rubbed on the surface and extinguishing the fire. * 4 Weather resistance Based on a continuous 500-hour sunshine weather meter test. * 5 Pencil hardness Pencil scratch value according to JIS k5400 (General paint test method), based on the manual scratching method. * 6 Boiling resistance test Based on confirmation of abnormal surface condition after boiling for 2 hours. * 7 Alkali resistance test 30% caustic soda is dropped on the surface, and after 24 hours, it is washed with water and then judged by the presence or absence of surface abnormality.

[0029]

The composition according to the present invention comprises a triazine ring-containing (meth) acrylate prepolymer and an isocyanate compound. The composition is impregnated or coated on a substrate such as a nonwoven fabric. It can be easily formed into a decorative board or the like by reacting it into a prepreg that can be handled and then hot-pressed.However, since it is a composition that does not contain a solvent, it does not need to be dried and it is condensed during molding. Since there is no generated gas such as water, there is no need to perform operations such as degassing during molding, and the process leading to molding can be simplified. Also,
The molded product using the composition has a structure in which the triazine ring skeleton is cross-linked with isocyanate via an acrylate moiety, so that in addition to the characteristics of the melamine resin such as hardness and heat resistance, it also has chemical resistance, weather resistance and boiling resistance. A molded article having excellent performance is obtained. Particularly, the acid resistance is a property that cannot be obtained with other resins, and thus it is most suitable for a laboratory tabletop and the like.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // B29K 75:00 B29K 75:00 105: 06 105: 06 C08L 75:12 C08L 75:12 F term (reference) 4F072 AB02 AB03 AB09 AB29 AD09 AD43 AG03 AH21 AJ04 AJ11 AK05 AK14 AL01 AL09 4F204 AA38 AA42 AG01 FA01 FB01 FF01 FG03 FN11 FN15 FQ01 4J011 PA30 PA95 PC02 4J027 AG01 AG03 AG22 AG24 AG25 CA08 DA03 CA08 DA08 DC17 DC19 DC23 DC42 DP18 FA01 FA02 FB01 FB04 FC01 FD01 HA01 HA06 HA07 HB06 HB07 HC01 HC02 HC03 HC25 HC32 HC34 HC35 HC44 HC46 HC52 JA41 JA43 JA45 JA46 LA24 QB14 QB17 QC08 RA05

Claims (3)

[Claims] 1. A method comprising a triazine ring-containing (meth) acrylate prepolymer synthesized from an aminotriazine compound, formaldehyde and hydroxy (meth) acrylate, an isocyanate compound and unreacted hydroxy (meth) acrylate. Resin composition. 2. A solid which can be handled by reacting a triazine ring-containing (meth) acrylate prepolymer synthesized from an aminotriazine compound, formaldehyde and hydroxy (meth) acrylate with an isocyanate compound and unreacted hydroxy (meth) acrylate. A method of manufacturing a decorative board, which comprises forming a shape and then heating and applying pressure. 3. A solid which can be handled by reacting a triazine ring-containing (meth) acrylate prepolymer synthesized from an aminotriazine compound, formaldehyde and hydroxy (meth) acrylate with an isocyanate compound and unreacted hydroxy (meth) acrylate. A decorative plate having a shape and being formed by heating and pressing.