JP2001288444A - Impregnating and adhesive bonding resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin-impregnating and adhesive resin composition having both hardness and toughness, excellent stability and water-diluting properties, good workability, excellent various strengths not only in the ordinary state but also in high humidity and wetting states, excellent folding resistance and impact resistance. SOLUTION: The impregnating or adhesive resin composition can be obtained by the condensation reaction of (A) 50-99 wt.% (solids content) aminoplast resin of at least one kind of, a melamine/formaldehyde resin, a melamine/glyoxal resin, a urea/formaldehyde resin, a urea/glyoxal resin, a carbamimide/ formaldehyde resin, a benzoguanamine/formaldehyde resin, a glycol/urea resin with (B) 1-50 wt.% (solids content) poly-alkylene glycol mono(meth)allyl ether under an alkaline condition under an alkaline condition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for resin impregnation of paper or wood, or a resin composition for an adhesive, and more specifically, a decorative board, WPC for furniture or building materials, etc.
A resin composition used as an impregnating resin or a resin composition for an adhesive when manufacturing a laminated board such as a board, or a heat-resistant inorganic board such as a rock wool board, a glass fiber mat, an asbestos board, and a secondary processing ( The present invention relates to a resin composition suitably used in producing a heat-resistant inorganic material sound-absorbing plate, a heat-resistant inorganic decorative plate, a heat-resistant inorganic decorative sound-absorbing plate, a tatami mat, and the like obtained by surface treatment. More specifically, it exhibits useful properties as the above-mentioned various impregnating resin compositions or adhesive resin compositions due to its excellent stability and water dilution stability, and also has a radical reaction crosslinkability by light and heat and thermosetting. The cured product has both hardness, flexibility, impact resistance, chemical resistance, water resistance and moisture resistance,
The present invention relates to an impregnating and bonding composition containing an allyl ether-modified aminoplast resin that imparts nonflammable physical properties.

[0002]

2. Description of the Related Art Conventionally, as a resin composition for impregnation or a resin composition for an adhesive as described above, for example, an aminoplast resin or a phenol resin is used. However, these resin compositions are hard and brittle with conventional aminoplast resins and phenolic resins as paper impregnating resins, for example, when producing decorative boards, lack flexibility and toughness, and have poor resistance to bending. Therefore, there has been a problem that it is easily broken at the time of bending.

Further, in order to improve these hard and brittle properties, the terminal group of the melamine resin is modified with acrylic to give an acrylic double bond, and toughness and water resistance are obtained by radical polymerization of the terminal double bond. Although the method of improving the physical properties of is also performed, the acrylic-modified melamine resin reacts sensitively to light and heat, the reactivity is too strong and poor stability, there is a limit in water dilutability, Workability was extremely poor.

[0004] When a phenolic resin is used for such a purpose, there are problems that curing is slow, workability is inferior, hard and brittle, and that the impregnated paper is discolored. On the other hand, in the production of rock wool plates, rock wool sound absorbing plates, rock wool decorative sound absorbing plates, etc., aminoplast resins or resins obtained by blending an acrylic emulsion with aminoplast resins are generally used. In addition, various aminoplast resins are generally impregnated with sizing boards and paperboards used as materials for tatami mats and core materials for various building materials.

[0005] However, these conventional aminoplast resins are impregnated with a resin composition obtained by blending an acrylic emulsion with an acrylic emulsion, and are not only inferior in strength and flexibility under ordinary conditions, but also in water resistance, high temperature, and the like.
There were problems such as inferior strength and flexibility under high humidity.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition for impregnation, such as a decorative board, having both the hardness and toughness characteristic of the thermosetting resin of aminoplast resin and phenol resin. In the case of processing of impregnated paper used for, it is excellent in stability and water dilutability, workability is good, not only physical properties of impregnated paper in normal conditions, but also excellent strength in high humidity and wet conditions Decorative panels with excellent bending resistance and impact resistance.In addition to rock wool ceiling panels, not only physical properties under normal conditions, but also various strengths under high humidity and wet conditions, flexibility and impact resistance. Provide resin compositions for resin impregnation and adhesives that can provide the required hardness and various strengths as core materials when impregnated into a zinc board or paper board as a core material even with a tatami core, etc. It is in.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that: [1] 50 to 99% by weight of aminoplast resin (A)
A resin composition for impregnation or an adhesive obtained by subjecting a polyalkylene glycol mono (meth) allyl ether (B) to 1 to 50% by weight (solid content) to a condensation reaction under alkaline conditions. [2] The aminoplast resin (A) is a melamine-formaldehyde resin, a melamine-glyoxal resin, a urea-formaldehyde resin, a urea-glyoxal resin,
The resin composition for an impregnation or adhesive according to the above [1], which is at least one of a carbamide-formaldehyde resin, a benzoguanamine-formaldehyde resin, and a glycol-urea resin. [3] The resin composition for impregnation or the adhesive according to the above [1], wherein the polyalkylene glycol mono (meth) allyl ether (B) is polyethylene glycol monoallyl ether or polypropylene glycol (meth) allyl ether. And [4] a method using the resin composition according to [1] above as a resin for impregnation or as an adhesive used in the production of a decorative board, a WPC board, a rock wool board, a secondary processing thereof, or a tatami core. Has solved the above-mentioned problem.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The aminoplast resin (A) in the composition of the present invention imparts thermosetting properties to the resin composition,
It is an essential component for maintaining the hardness of the processed product in the above-mentioned various uses in the normal state and the wet state, and the water resistance and moisture resistance of the processed product. Examples of the aminoplast resin (A) that can be used in the present invention include known melamine-formalin resins, melamine-glyoxal resins, urea-formalin resins, urea-glyoxal resins, carbamide-formalin resins, benzoguanamine-formalin resins, glycol- Urea resins and the like can be mentioned. Among these, the melamine-formaldehyde resin can be most suitably used in all aspects such as heat resistance, fire resistance and strength. The amount used is 50 to 99 in the total solid components.
%, Preferably 70 to 98% by weight. When the amount of the aminoplast resin (A) used is less than 50% by weight of the total solid components, the hardness when the resin composition is solidified is low, and other physical properties such as normal strength, moisture resistance and water resistance are also low. Low,
Hardness, various strengths, and nonflammability of a processed product produced after processing using the resin composition are all inferior. The amount of the aminoplast resin (A) used was 99% by weight of the total solid components.
If more, the resulting composition has the disadvantage that it is hard, brittle and lacks flexibility.

The polyalkylene glycol mono (meth) allyl ether (B) in the composition of the present invention imparts radical polymerizable photocurability and thermosetting to the composition, and is thermally crosslinked with an aminoplast resin. It forms a crosslinked product of a water-soluble resin, and further serves to impart flexibility and water retention. The used amount is 1 to 50% by weight, preferably 2 to 30% by weight based on all the components used. Examples of the polyalkylene glycol mono (meth) allyl ether (B) of the present invention include polyethylene glycol monoallyl ether, propyleneylene glycol monoallyl ether and the like. Among them, polyethylene glycol monoallyl ether having a molecular weight of about 350 to 600 is most preferable from the viewpoint of the operation and the physical properties of the obtained product. When the amount of the polyalkylene glycol mono (meth) allyl ether (B) used is less than 1% by weight of the total solid components used, the flexibility and water retention of the composition are poor, and the composition was produced using the composition. In the case of a processed product, for example, a decorative board, it has low resistance to bending, and is hard and brittle.

In the condensation reaction of these resin compositions, for example, when a melamine-formalin resin generally well known as an aminoplast resin (A) is used, a conventional method for producing an ordinary aminoplast resin is used. After producing a melamine-formaldehyde resin based on this method, the following method is used. First, melamine and formaldehyde blended in a predetermined ratio are reacted with alkali to convert melamine into methylol (A). Next, this is reacted with polyalkylene glycol mono (meth) allyl ether (B) under strong alkalinity. Next, in order to maintain stability, methanol is added to perform a methoxylation reaction. Finally, the pH is adjusted to alkaline to obtain the desired allyl ether-modified aminoplast resin. Other allyl ether-modified aminoplast resins can be produced in a similar manner.

The produced resin may be used as it is as an impregnating resin or an adhesive resin for various kinds of processing, or the resulting resin is concentrated under reduced pressure to a certain concentration, as is generally the case with general aminoplast resins. Then, after removing excess water, methanol, formaldehyde, etc., it may be used for various processes. In addition, the resin has the property of being stably dilutable with water and has excellent storage stability, but has a radical polymerizable double bond in the molecule, so that light or heat can be obtained without adding a photopolymerization initiator. In some cases, it may be polymerized and cured during storage, leading to gelation, so that it may be necessary to add a small amount of a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether (methquinone).

The aminoplast resin (A) of the present invention and the polyalkylene glycol mono (meth) allyl ether (B) are blended in the above ratio, and the mixture is heated at a temperature of 50 to 110 ° C. for 5 minutes to 1 hour, preferably 75 to 110 hours. The condensation reaction is carried out at 90 ° C. for 5 to 20 minutes in the presence of an alkali catalyst to oligomerize. The resin composition that has undergone the condensation reaction has excellent dilutability, and after being diluted to an appropriate concentration as necessary, paper, wood,
Rolls, brushes or other inorganic materials such as glass fiber mats and rock wool plates are applied or impregnated by impregnation, and further heated to make the decorative resin a completely cured resin with a network structure. It can be processed into a sound-absorbing plate, core material, sheathing board and the like. The processed product thus obtained is a cured product which is hard and has excellent flexibility, toughness and impact resistance, and does not easily break even when bent.

[0013]

The present invention will be described more specifically with reference to the following examples and comparative examples, but the present invention is not limited to these examples. (Example 1) In preparing a resin-impregnated paper, an allyl ether-modified aminoplast resin was prepared by the following formulation and procedure. First, the raw materials used are shown in Table 1.

[0014]

[Table 1]

Is charged into a reaction vessel. pH9.
The reaction is carried out at 4 to 10.0 at 80 ° C. for 10 minutes to form methylol. Next, is added, and the mixture is further reacted at 80 ° C. for 20 minutes to perform an addition reaction of glycol. Next,
A methoxylation reaction was carried out at 73 to 75 ° C. for 80 minutes, and after cooling, the pH was adjusted to 10 to 11 and further added to obtain an allyl ether-modified aminoplast resin.

Example 2 An allyl ether-modified aminoplast resin was obtained in the same manner as in Example 1, except that the average molecular weight of the allyl ether-modified monoallyl ether used in Example 1 was changed to 200. . Example 3 The amount of the polyethylene glycol monoallyl ether (average molecular weight 450) used in Example 1 was 1
Except that the amount was changed to 00 g, the same procedure as in Example 1 was carried out to obtain an allyl ether-modified aminoplast resin.

(Comparative Example 1) In the aminoplast resin of Example 1, allyl ether-modified monoallyl ether was not used, and the methylolation reaction product shown in Table 1 was used. (Comparative Example 2) In the aminoplast resin of Example 1,
Instead of polyethylene glycol monoallyl ether, a methacrylic acid-modified polyethylene glycol ester using methacrylic acid was used. The resin had poor stability and could not be diluted, so that impregnation was not possible.

Comparative Example 3 A phenol resin was used.
The processed product was colored brown, and was not worth the commodity. Comparative Example 4 Example 1 was repeated except that 600 g of polyethylene glycol monoallyl ether was used in the production of the allyl ether-modified aminoplast resin in Example 1.
Allyl ether-modified aminoplast resin was obtained in the same manner as described above.

[Impregnation Test on Paper] Using the allyl ether-modified aminoplast resin produced in the above Examples and Comparative Examples, the paper was impregnated under the following conditions. The methacrylate resin of Comparative Example 2 did not have any dilutability in water and could not be impregnated. Further, the impregnated paper of the phenolic resin of Comparative Example 3 turned brownish and was judged to have no commercial value, and thus the physical properties of the processed product were not measured. Examples 1 to 3 and Comparative Example 1
Table 2 shows the results of evaluating the physical properties of the impregnated papers No. 4 to No. 4.

[Test Conditions for Paper Impregnation] Substrate No. No. manufactured by Toyo Filter Co., Ltd. 2 Filter paper Impregnation conditions Impregnation amount 40-45% (vs. filter paper) Pre-drying 80 ° C / 10min. Press curing 140 ° C / 10min. It measured according to. 50mm x 150mm width test piece Span width 100mm Flexural strength 5mm / min

(Impregnated resin formulation) Resin 100 g Curing catalyst (p-toluenesulfonic acid) 2 g 20% APS (radical polymerization catalyst) 0.15 g Water α Total 200 g

[0022]

[Table 2]

[0023]

The present invention has excellent storage and transport stability as an impregnating resin for organic polymer plates such as paper and non-woven fabric, or heat-resistant inorganic plates such as rock wool plates, glass fiber mats and asbestos plates. It is a resin composition that is hydrophilic and can be easily diluted with water. And when it is used by impregnating the above various plate materials, it is easily cured by radical crosslinking reaction and thermal curing reaction, and the cured product obtained has high strength, flexibility, impact resistance, and heat curing Chemical resistance as a conductive resin,
The cured product has water resistance, moisture resistance, and nonflammability. These include decorative boards used for furniture and building materials, WP
It becomes a material having excellent performance as a C plate, a reinforcing material, a sound absorbing plate, and the like.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09J 171/00 C09J 171/00 B // C08G 12/42 C08G 12/42 F-term (Reference) 2B230 AA16 AA27 CB07 CB12 CB25 CC11 EB28 4J002 BN171 BP031 CC131 CC161 CC181 CC191 CC211 CC231 CC241 GJ01 4J033 EA02 EA09 EA12 EA23 EA35 EA45 EA62 EA72 EB16 EC03 HA14 HB09 4J040 EB111 EB121 MA05 07 EB141 MA07

Claims (4)

[Claims] 1. An aminoplast resin (A) of 50 to 99% by weight (solid content) and a polyalkylene glycol mono (meth) allyl ether (B) of 1 to 50% by weight (solid content) are subjected to a condensation reaction under alkaline conditions. The resin composition for impregnation or adhesive obtained by the above. 2. The aminoplast resin (A) is a melamine-formaldehyde resin, a melamine-glyoxal resin, a urea-formaldehyde resin, a urea-glyoxal resin, a carbamide-formaldehyde resin, a benzoguanamine-formaldehyde resin, or a glycol-urea resin. The resin composition for impregnation or adhesive according to claim 1, which is at least one kind. 3. Polyalkylene glycol mono (meth)
The resin composition for impregnation or adhesive according to claim 1, wherein the allyl ether (B) is polyethylene glycol monoallyl ether or polypropylene glycol (meth) allyl ether. 4. The resin according to claim 1, which is used as a resin for impregnation or an adhesive used in producing a decorative board, a WPC board (wood-plastic composite), a heat-resistant inorganic board, a secondary processing thereof, or a tatami core. A method using a resin composition.