KR101648460B1 - Resin composite for binder of heat insulating material, Copolymer resin for binder of heat-insulating material using the same, Binder resin for heat insulating material containing that, and Eco-heat insulating material having permeable water-resistance - Google Patents

Abstract

The present invention relates to a copolymer resin composition for insulating binders, a copolymer resin for insulating binders produced by using the same, an insulating binder resin, and an insulating material using the same. More specifically, by using the insulating binder resin containing a copolymer for insulating binders, it is possible to produce insulating materials with excellent compressibility and water resistance without release of substances harmful to human body such as formalin.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for a heat insulating binder, a copolymer resin for a heat insulating binder, a binder resin for a heat insulating material containing the binder resin, and an eco- using the same, Binder resin for containing the heat insulating material, and having an eco-heat insulating material having permeable water-resistance}

The present invention relates to a copolymer resin composition for a heat insulating binder, a copolymer resin for a heat insulating binder, a binder resin containing the same, an environmentally friendly heat insulating material excellent in water resistance using the binder resin, and a method for producing the same.

Generally, the wall surface to which the wallpaper is attached is made of concrete or brick used in the building, and there is a minute pore, so that the cool air or heat is introduced into the interior of the building from the outside. Therefore, in order to block the entrance of cold air or heat to the building, the heat insulating material is attached to the wall surface before the wallpaper is installed, or is embedded in the wall of the building.

As described above, the heat insulation in a building is a very important function in providing a pleasant environment by enhancing the efficiency of cooling and heating. It is preferable to use a material having a low thermal conductivity as the heat insulation material for this purpose. A heat insulating effect is obtained by using the heat insulating property of the air existing in the micro pores formed by the porosity so as to have the porosity in order to reduce the thermal conductivity.

Foamed styrene which is not only inexpensive but also easy to purchase is widely used as a heat insulating material adhered to a wall, and Korea Patent No. 0237975 discloses a method of producing a heat insulating material using waste urethane foam and expanded polystyrene , Discloses a method for manufacturing a heat insulating material obtained by mixing and molding pulverized urethane foam and expanded polystyrene. However, the conventional insulating material such as foamed styrene, for example, merely effects heat insulation by reducing the thermal conductivity depending on the heat insulating property of air existing in many micropores. Therefore, the effect is limited, It has a problem that it can not meet the demand.

In addition, asbestos, polyurethane foam, expanded polystyrene (EPS), and extruded polystyrene (EXP) have been used as a heat insulating material to be embedded in a wall of a building. However, in the case of the above-mentioned asbestos, drinking the powder through the breath has been identified as a substance capable of causing malignant tumors in lung cancer, lung disease, pleura or pleura and is designated as a carcinogen by the World Health Organization (WHO) have. In addition, insulation materials such as polyurethane foam, EPS, and EXP have recently been recognized as materials that are not flame retardant or incombustible, and are not suitable for various fire prevention regulations. Therefore, it is urgent to replace the conventional insulation.

Insulation materials using glass fibers such as glass wool or lacquer have been developed and applied in place of conventional insulation materials. In the case of existing insulation materials using glass fibers, harmful components such as formaldehyde, phenol, and formalin There is a problem that these harmful substances are derived from the binder resin used for producing the insulating material. Accordingly, a heat insulating material using an acrylic binder resin improved the conventional binder resin for a heat insulating material has been developed. When the heat insulating material is required to have a high heat resistance, in particular, a high water resistance is required in the case of a heat insulating material for construction and / or a ship. However, in the case of the acrylic binder resin, phenol, formalin and the like are not used, There is a problem that the heat resistance and the water resistance are lower than those of the resin.

Therefore, it is urgent to develop a binder material for an insulating material having excellent physical properties such as heat resistance, water resistance, and the like, which are eco-friendly without the emission of harmful components in the human body.

Korea Publication No. 10-2013-0012489 (2013.02.04) Republic of Korea Pub. No. 10-2007-0026468 (2007.03.08) Republic of Korea Publication No. 10-2003-0061541 (July 22, 2003)

It is an object of the present invention to provide a binder material capable of producing a heat insulating material excellent in physical properties while preventing the release of environmentally harmful substances, which is a problem of a conventional binder material for a heat insulating material, and also to provide a heat insulating material having excellent water resistance .

In order to solve the above-mentioned problems, the present invention relates to a copolymer resin composition for a heat insulating material binder, which comprises a compound represented by the following formula (1), a compound represented by the following formula (2), a first initiator, alkylol acrylamide) and water; And dextrin; A second initiator; And water.

[Chemical Formula 1]

Wherein R ¹ is a linear alkyl group having ¹ to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 5 to 10 carbon atoms, R ² is a hydrogen atom, A straight chain alkyl group, a C3 to C5 branched alkyl group or a C5 to C10 aryl group.

(2)

In Formula 2, R < ^{1 >} And R ² is as independent, R ¹ And R ² are each a hydrogen atom, a straight chain alkyl group having 1 to 3 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, or a C5 to C10 aryl group.

In one preferred embodiment of the present invention, the copolymer resin composition for thermal insulation binders of the present invention may include the dextrin and the mixture at a weight ratio of 1: 1.2 to 5.5.

In one preferred embodiment of the present invention, the mixture is prepared by mixing 10 to 50 parts by weight of the compound represented by Formula 2, 1 to 7 parts by weight of the first initiator, 5 to 80 parts by weight of alkylol acrylamide and 80 to 250 parts by weight of water.

In one preferred embodiment of the present invention, the first initiator is selected from the group consisting of sodium persulfate, Ammonium persulfate, Potassium persulfate, t-butyl hydroperoxide, sec-butyl hydroperoxide, and the like. In the present invention, it is preferable to use at least one selected from the group consisting of t-butyl hydroperoxide and sec-butyl hydroperoxide.

As a preferred embodiment of the present invention, in the copolymer resin composition for thermal insulation binders of the present invention, the N-alkylol acrylamide is at least one selected from the group consisting of N-methylol acrylamide, N-ethylol acrylamide and N-propyl acrylamide , And the like.

In a preferred embodiment of the present invention, in the copolymer resin composition for a thermal insulation binder of the present invention, the second initiator is sodium hypophosphite, sodium persulfate, ammonium persulfate ), At least one selected from the group consisting of potassium persulfate, t-butyl hydroperoxide and sec-butyl hydroperoxide. have.

In one preferred embodiment of the present invention, in the copolymer resin composition for a heat insulating material binder of the present invention, the second initiator is used in an amount of 4 to 20 parts by weight based on 100 parts by weight of the destyrene.

Another object of the present invention is to provide a copolymer resin for a thermal insulation binder, which comprises a copolymer comprising a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4) and a repeating unit represented by the following formula .

(3)

Wherein R ¹ is a hydrogen atom, a straight-chain alkyl group of C ¹ to C 5 or a C 5 to C 10 cycloalkyl group,

[Chemical Formula 4]

Wherein R ¹ is a straight-chain alkyl group having ¹ to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 5 to 10 carbon atoms, R ² is a hydrogen atom, A branched alkyl group, a C3 to C5 branched alkyl group or a C5 to C10 aryl group,

[Chemical Formula 5]

In Formula 5, R < ^{1 >} And R ² is as independent, R ¹ And R ² are each a hydrogen atom, a straight chain alkyl group having 1 to 3 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, or a C5 to C10 aryl group.

As a preferred embodiment of the present invention, in the copolymer resin for thermal insulation binder of the present invention, the copolymer includes a repeating unit represented by the following formula (6), and the copolymer has a weight average molecular weight of 3,000 to 50,000 .

[Chemical Formula 6]

Wherein R ¹ is a hydrogen atom, a straight-chain alkyl group having ¹ to 5 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms, R ² is a straight-chain alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cycloalkyl group or an aryl group of C5 ~ C10 of C10, R ^3, R ⁴ and R ⁵ as being independent, R ^3, R ⁴ and R ⁵ Each Hydrogen atom, X: Y: Z = 1: 1.0 to 6.0: 0.08 to 0.5, wherein X, Y and Z are each a linear alkyl group of C1 to C3, a branched alkyl group of C3 to C5 or an aryl group of C5 to C10, to be.

In one preferred embodiment of the present invention, the copolymer resin for thermal insulation binders of the present invention has a viscosity of 15 to 100 cps (25 ° C) and a pH of 2.5 to 5.0.

In one preferred embodiment of the present invention, the copolymer resin for a heat insulating material binder of the present invention has a thermal decomposition rate of 60% to 70% at 600 ° C as measured by a thermogravimetry analysis.

Another object of the present invention is to provide a method for producing a copolymer resin for a heat insulating binder as described above, comprising the steps of: preparing a dextrin mixture by mixing, stirring and mixing dextrin, a second initiator and water; A step for raising the dextrin mixture to 75 ° C to 85 ° C; A mixture comprising the compound represented by the formula (1), the compound represented by the formula (2), the first initiator, the N-alkylol acrylamide and water is added to the dextrin mixture at 75 ° C to 85 ° C Adding and stirring, and performing a copolymer reaction to prepare a solution containing the copolymer; And adjusting the pH of the solution to 2.5 to 5.0 after adjusting the solid content of the solution.

In a preferred embodiment of the present invention, water is added to the solution so that the solid content of the solution becomes 40% to 45% in step 4.

In a preferred embodiment of the present invention, in step 4, the pH is selected from the group consisting of tri- (C1-C3 alkyl) amine, ethanolamine, diethanolamine, ethylene glycol, diethylene glycol , Propylene glycol, neopentin glycol, butylene glycol, glycerin, and a carbonate polyol.

Another object of the present invention is to provide a binder resin for a heat insulating material, which comprises the above-described various types of copolymer resins for heat insulating binders.

In one preferred embodiment of the present invention, the binder resin for a heat insulating material of the present invention may contain a silane additive, an organic amine and water in addition to the above-mentioned copolymer resin for heat insulating binder.

In one preferred embodiment of the present invention, the binder resin for a heat insulating material of the present invention comprises 0.05 to 1 part by weight of a silane additive, 0.1 to 2 parts by weight of the organic amine, 700 parts by weight.

In a preferred embodiment of the present invention, the silane additive is selected from the group consisting of glycidoxy (C2 to C5 alkyl) tri (C1 to C2 alkoxy) silane, 3 amino (C2 to C5 alkyl) ) Silane and N- (2-amino (C1 to C3 alkyl) -3-amino (C2 to C5 alkyl) tri (C1 to C2 alkoxy) silane .

In one preferred embodiment of the present invention, the organic amine is selected from the group consisting of ammonium hydroxide, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, and ammonium chloride. , And the like.

In one preferred embodiment of the present invention, the binder resin for the heat insulating material may further include additives including at least one selected from an anti-wetting agent, an antibacterial agent, a crosslinking density enhancer, a deodorant, a dust inhibitor, an antioxidant and an antifreezing agent.

Another object of the present invention is to provide an eco-friendly thermal insulation material excellent in water resistance. The heat insulation material of the present invention is a heat insulation material free from the release of formalin or phenol-formalin. And a glass fiber.

In one preferred embodiment of the present invention, the thermal insulation material of the present invention may have a compressibility of 19.5% to 25% when measured according to the following formula (1).

[Equation 1]

In the above equation 1, D ₁ is a width 400mm, 400mm and vertical steel plate over a test piece having a thickness of 50mm, move up the (W 400mm, 400mm vertically), raise the 20㎏ weight to the upper surface of the steel plate, and then, test pieces after 5 minutes D _o is an average value of the thickness of the middle portion of the test piece before the weight is increased.

As a preferred embodiment of the present invention, the heat insulating material of the present invention may have a water absorption rate of 6% or less when measured according to the following formula (2).

&Quot; (2) "

In the formula (2), M ₁ is a test piece having a width of 200 mm, a length of 150 mm and a thickness of 50 mm, placed at a position of 30 mm below the water surface of 25 (± 5) ° C. and allowed to stand for 2 hours. M _o is the weight of the test piece before putting the test piece into water, V is the volume of the test piece before putting into water and δ is the specific gravity of water.

In one preferred embodiment of the present invention, the heat insulating material of the present invention has a weight retention rate of 80% to 90% when measured according to the following equation (3).

&Quot; (3) "

In Equation (3), T ₁ is a test piece having a width of 50 mm, a length of 50 mm and a thickness of 50 mm, placed at a position of 30 mm below the surface of water at 100 ° C. and allowed to stand for 2 hours. Lt; 0 > C in a vacuum oven for 3 hours, and T _o is the weight of the test piece before putting in water.

delete

Another object of the present invention is to provide a method for producing an environmentally friendly heat insulating material having excellent water resistance, comprising the steps of: (1) preparing a binder resin comprising the above-mentioned copolymer resin for heat insulating binder, silane additive, organic amine and water; Spraying the binder resin onto the glass fiber; And curing at 220 DEG C to 250 DEG C for 2 minutes to 10 minutes; And a control unit for controlling the display unit.

The heat insulating material made of the binder resin including the copolymer resin for a heat insulating material binder of the present invention has excellent compressibility and water resistance, and in particular, does not emit environmentally harmful substances such as formaldehyde, phenol, and formalin, It is possible to provide a highly environmentally friendly heat insulating material and a heat insulating material.

The term " C1 ", "C2 ", etc. used in the present invention means a carbon number. For example," C1 to C5 alkyl "means an alkyl group having 1 to 5 carbon atoms.

The resin for the heat insulating material binder of the present invention will be described first.

The resin for a binder for a heat insulating material of the present invention comprises a copolymer resin, wherein the copolymer resin comprises a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4) and a repeating unit represented by the following formula Polymer, and preferably the copolymer for thermal insulation binders comprises a copolymer having repeating units represented by the following formula (6).

(3)

In the above formula (3), R ¹ is a hydrogen atom, a straight-chain alkyl group having ¹ to 5 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms, preferably R ¹ is a hydrogen atom or a linear alkyl group having ¹ to 3 carbon atoms, ¹ is a hydrogen atom or a methyl group.

[Chemical Formula 4]

In Formula 4, R ¹ is an aryl group of C1 ~ C10 straight alkyl, C3 ~ C10 crushing alkyl group, C5 ~ C10 cycloalkyl group or a C5 ~ C10 of, preferably, R ¹ is a straight of C1 ~ C5 A branched alkyl group having 3 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, or a C5 to C7 cycloalkyl group. More preferably, R ¹ is a linear alkyl group having ¹ to 3 carbon atoms or an isopropyl group. In formula (4), R ² is a hydrogen atom, a linear alkyl group having 1 to 3 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, or a C 5 to C 10 aryl group, preferably R ¹ is a hydrogen atom or a Chain alkyl group, more preferably R ¹ is a hydrogen atom or a methyl group.

[Chemical Formula 5]

In Formula 5, R < ^{1 >} And R ² is as independent, R ¹ And R ² each is an aryl group, a hydrogen atom, C1 ~ C3 straight alkyl, C3 ~ C5 alkyl group or a C5 ~ C10 milling of, preferably R ¹ And each of R ² is preferably a hydrogen atom or a straight-chain alkyl group having ¹ to 3 carbon atoms, and more preferably, R ¹ is a hydrogen atom or a methyl group.

[Chemical Formula 6]

In Formula 6, R ¹ is a hydrogen atom, a linear alkyl group having ¹ to 5 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms, preferably a hydrogen atom or a straight-chain alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom Or a methyl group. In addition, the R ² is an aryl group of C1 ~ C10 straight alkyl, C3 ~ C10 crushing alkyl group, C5 ~ C10 cycloalkyl group or a C5 ~ C10 of, preferably, R ¹ of formula (6) is a C1 ~ C5 A branched alkyl group having from 3 to 5 carbon atoms, or a cycloalkyl group having from 5 to 7 carbon atoms. More preferably, R ¹ is a straight-chain alkyl group having ¹ to 3 carbon atoms or an isopropyl group. Further, R ³ , R ⁴ and R ^{5 in the general} formula (6) are independent of each other, and R ³ , R ⁴ and R ⁵ Each Hydrogen atom, A straight chain alkyl group of C1 to C3, a branched alkyl group of C3 to C5 or an aryl group of C5 to C10, preferably R ³ , R ⁴ and R ⁵ Each is a hydrogen atom or a straight-chain alkyl group having from 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.

The X, Y, and Z in the formula (6) may be a molar ratio of the monomer, X: Y: Z = 1: 1.0 to 6.0: 0.08 to 0.5, and preferably 1: 1.0 to 5.8: 0.08 to 0.35 Lt; / RTI >

The copolymer of the thermoplastic binder resin may have a weight average molecular weight of 3,000 to 50,000, preferably a weight average molecular weight of 15,000 to 35,000. If the weight average molecular weight of the copolymer is less than 3,000, , Resilience and water resistance may be deteriorated. If the weight average molecular weight exceeds 50,000, there is a high possibility of causing a high viscosity and gelation, and there may be a problem that a defective product is formed due to a lack of adhesion.

In addition, when measured by a thermogravimetry analysis, the copolymer may have a thermal decomposition rate of 60% to 70%, preferably 62% to 68% at 600 ° C.

The copolymer resin for a heat insulating material binder may have a viscosity of 15 to 100 cps (25 ° C), preferably 20 to 80 cps (25 ° C), and more preferably 20 to 60 cps have.

The copolymer resin for the heat insulating material binder may have a pH of 2.5 to 5.0, preferably 3.0 to 4.0.

Such a copolymer resin for thermal insulation binders is a mixture comprising a compound represented by the following formula (1), a compound represented by the following formula (2), a first initiator, an N-alkylol acrylamide and water; And dextrin; A second initiator; And water. ≪ / RTI >

[Chemical Formula 1]

In the above Formula 1, R ¹ is an aryl group of C1 ~ C10 straight alkyl, C3 ~ C10 crushing alkyl group, C5 ~ C10 cycloalkyl group or a C5 ~ C10 of, preferably, R ¹ is a C1 ~ C5 A branched alkyl group having from 3 to 5 carbon atoms, or a cycloalkyl group having from 5 to 7 carbon atoms. More preferably, R ¹ is a straight-chain alkyl group having ¹ to 3 carbon atoms or an isopropyl group. R ² in formula (1) is a hydrogen atom, a linear alkyl group having 1 to 3 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, or an aryl group having 5 to 10 carbon atoms. Preferably, R ² is a hydrogen atom or a Chain alkyl group, more preferably R ² is a hydrogen atom or a methyl group.

(2)

In Formula 2, R < ^{1 >} And R ² is as independent, R ¹ And R ² each is an aryl group, a hydrogen atom, C1 ~ C3 straight alkyl, C3 ~ C5 alkyl group or a C5 ~ C10 milling of, preferably R ¹ And R ² are each a hydrogen atom or a straight-chain alkyl group having ¹ to 3 carbon atoms, more preferably R ¹ is a hydrogen atom or a methyl group.

In the composition of the present invention, it is preferable that the dextrin and the mixture are contained in a weight ratio of 1: 1.2 to 5.5, preferably 1.35 to 5.3. When the content of the mixture is less than 1.2, Water resistance and restitution force may be deteriorated. If it exceeds 5.5 weight ratio, there may be a problem that the injection nozzle is cured due to poor product molding and shortening of curing time due to viscosity increase.

Further, in the composition of the present invention, the mixture may contain 10 to 50 parts by weight of the compound represented by the general formula (2), 1 to 7 parts by weight of the first initiator, 1 to 7 parts by weight of the N-alkyl 5 to 80 parts by weight of acrylamide and 80 to 250 parts by weight of water, preferably 12 to 35 parts by weight of the compound represented by the formula (2), 1.5 to 1.5 parts by weight of the first initiator 1.5 5 to 50 parts by weight of N-alkylol acrylamide, and 80 to 200 parts by weight of water.

If the amount of the compound represented by the general formula (2) is less than 10 parts by weight, the molecular structure of the binder resin may be in a tandem type so that strength, water resistance and heat resistance can not be secured. And molecular weight increase due to polymerization may cause defective molding, clogging of pipes, and hardening of the inside of the nozzle.

The first initiator is added to disperse the initial heat and induce a stable reaction. As the first initiator, sodium persulfate, Ammonium persulfate, Potassium persulfate t-butyl hydroperoxide and sec-butyl hydroperoxide may be used singly or in combination of two or more kinds. The amount of the used amount of If the amount is less than 1 part by weight based on 100 parts by weight of the compound represented by the formula (1), the reaction rate may become slow and the effect of initiating the reaction may not be exhibited. If the amount exceeds 7 parts by weight, The production yield of the desired copolymer may be lowered.

Also, the N-alkylol acrylamide is used for the cross-linking role between the in-line polymers, and the N-alkylol acrylamide is selected from the group consisting of N-methylol acrylamide, N-ethylol acrylamide and N-propyl acrylamide , Preferably at least one selected from N-methylol acrylamide and N-ethylol acrylamide, and more preferably N-methylol acrylamide. If the amount of the N-alkylol acrylamide used is less than 5 parts by weight based on 100 parts by weight of the compound represented by the general formula (1), there may be a problem that the crosslinking effect between molecules is lowered. If the amount is more than 80 parts by weight, There may be a problem of gelation due to high temperature, so it is preferable to use within the above range.

If the amount of water used in the mixture component is less than 80 parts by weight based on 100 parts by weight of the compound represented by the general formula (1), there may be a problem that mixing of components of the mixture does not occur well. If the amount is more than 250 parts by weight, The yield of the polymer may be lowered.

The composition of the present invention may further comprise a second initiator in addition to the mixture, and the second initiator may include sodium hypophosphite, sodium persulfate, ammonium persulfate, potassium One selected from the group consisting of potassium persulfate, t-butyl hydroperoxide and sec-butyl hydroperoxide may be used singly or in combination of two or more. . The amount of the second initiator may be 4 to 20 parts by weight, preferably 6 to 18 parts by weight based on 100 parts by weight of dextrin. At this time, if the amount of the second initiator used is less than 4 parts by weight, there may be a problem that the yield of the copolymer is lowered, and even if the amount is more than 20 parts by weight, the production yield is not increased.

In addition, the composition of the present invention may further comprise water in addition to the water, dextrin, mixture and second initiator contained in the mixture, wherein the water content is 100 to 450 parts by weight, preferably 100 to 450 parts by weight, May contain 130 to 380 parts by weight, more preferably 135 to 370 parts by weight. If the amount of water used is less than 100 parts by weight, the mixing of the dextrin and the mixture component may not be performed well, resulting in poor compatibility and low reactivity, a high solids content of more than 45% by weight, If it is used in excess of 450 parts by weight, the concentration of the solution may be lowered and the reaction rate may be rather low, and the solid content may be less than 40% by weight, which may result in a low adhesion rate.

A method for preparing a copolymer using the above-described copolymer resin composition for a thermal insulation binder will now be described in more detail. The first step is to prepare a dextrin mixture by mixing and stirring the dextrin, the second initiator and water. A step for raising the dextrin mixture to 75 ° C to 85 ° C; A mixture comprising the compound represented by the formula (1), the compound represented by the formula (2), the first initiator, the N-alkylol acrylamide and water is added to the dextrin mixture at 75 ° C to 85 ° C Adding and stirring, and performing a copolymer reaction to prepare a solution containing the copolymer; And adjusting the pH of the solution to 2.5 to 4.0 after adjusting the solid content of the solution. The copolymer resin for a thermal insulation binder of the present invention can be prepared by the following process.

In the manufacturing method of the present invention, the reason for raising the temperature of the dextrin mixture to 75 ° C to 85 ° C in step 2 is to increase the reaction rate between the compound represented by Chemical Formulas 1 and 2 and dextrin, , The reaction yield may be lowered. If the temperature is higher than 85 ° C, there may be a problem that the dextrin is converted into a paste due to the smoothing action of dextrin. It is also preferable that the copolymerization reaction of the three steps is carried out in the same temperature range as the temperature range of the two steps.

In the production method of the present invention, water may be added to the solution so that the solids content of the solution in Step 4 is 40 wt% to 45 wt%, preferably 41 wt% to 44 wt%.

In addition, in step 4, the solution is adjusted to a pH of 2.5 to 5.0, preferably 3.0 to 4.0. If the pH is less than 2.5, corrosion of production facilities due to product acidity may occur, , There may be a problem that the curing rate is delayed. Therefore, it is preferable to adjust the pH to the above range. The pH may be adjusted by a conventional pH adjusting agent used in the art, preferably tri- (C1-C3 alkyl) amine, ethanolamine, diethanolamine, It is preferable to adjust the pH using a pH adjusting agent comprising at least one selected from ethylene glycol, diethylene glycol, propylene glycol, neopentin glycol, butylene glycol, glycerin and carbonate polyol.

The binder resin for thermal insulation of the present invention, which comprises the above-described composition and a copolymer resin for an insulating binder prepared by the production method, may contain a silane additive, an organic amine and water in addition to the copolymer resin.

In the binder resin for a heat insulating material of the present invention, the silane additive serves to improve coupling and adhesion of glass fiber and / or glass fiber and other components as main components of the heat insulating material, 0.01 to 3 parts by weight, preferably 0.05 to 1 part by weight, more preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight of the polyisocyanate compound. If the amount of the silane additive is less than 0.01 part by weight, the amount of the silane additive used is too small to improve the coupling effect. If the amount of the silane additive is more than 3 parts by weight, the coupling effect is not improved.

As the silane additive, a silane coupling agent generally used in the art can be used, and preferably 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxy 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, Glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , Vinyltris (2-methoxyethoxy) silane, vinyltrichloro Silane, trimethylvinylsilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, ethyltriethoxysilane, n-propyltrimethoxy Silane, n-propyltriethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, octyltri T-butyldimethylchlorosilane, cyclohexylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylethyldimethoxysilane, t-butylmethyldimethoxysilane, decafluoro-1,1,2,2- ((Heptadecafluoro-1,1,2,2-tetrahydrodecyl) trimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltrimethoxysilane and 3-chloropropylmethyl dimethoxy silane Can be used singly or in combination of two or more.

In the binder resin for thermal insulation of the present invention, the water may be used in an amount of 300 to 700 parts by weight, preferably 400 to 600 parts by weight, based on 100 parts by weight of the copolymer resin. In this case, The viscosity of the binder resin becomes too high to cause a problem that the nozzle is clogged when injected into the glass fiber or hardened inside the pipe. When the amount of water used is more than 700 parts by weight, the viscosity becomes rather low and the glass fiber, which is the main component of the heat insulating material, There may be a problem in that the bonding force (or binding force) between them is lowered.

The binder resin for a heat insulating material of the present invention may further contain additives such as a humectant, an antibacterial agent, a crosslinking density enhancer, a dust inhibitor, a deodorant, an antioxidant and an antifreezing agent in addition to a copolymer, a silane additive, .

As the moisture absorbing agent, a general moisture absorbing agent used in the related art can be used. For example, poly (organosiloxane) can be used, and the amount thereof used does not affect the physical properties such as water resistance and compressibility of the heat insulating material It can be used within range.

As the antibacterial agent, additives commonly used in the art can be used. Examples of the antibacterial agent include 3-iodo-2-propyl-n-butylcarbamate, carbamic acid, butyl-3-iodo-2-propynyl ester IPBC), 2-bromo-2-nitropropane-1,3-diol, magnesium nitrate, 5-chloro-2-methyl-4-isothiazolin-3-one, magnesium chloride, It is possible to use a mixture of at least one selected from the group consisting of phenol, sodium salt, diiodomethyl-p-tolylsulfone, dibromoacetonitrile and 2,2-dibromo-3-nitrilopropionamide, The amount used can be used within a range that does not affect the physical properties such as water resistance and compressibility of the heat insulator.

Among the additives, the crosslinking density enhancer is to improve the degree of crosslinking of the binder resin, and is preferably selected from the group consisting of (C2 to C5 alkylol) amines, di (C2 to C5 alkylol) amines, tri (C2 to C5 alkylol) , (C1-C4 alkylamine) ethanol, and (C1-C4 alkylamine) propanol, and the amount thereof used does not affect the physical properties such as water resistance and compressibility of the heat insulating material You can use it within a range that does not.

Among the additives, the dust inhibitor is for suppressing generation of dusts that can be generated from the glass fiber during the heat insulating material manufacturing process. The dust inhibitor may be a conventional dust inhibitor used in the art. For example, natural dust, Can be used.

The antioxidant may be one selected from the group consisting of ethylamine, methylamine, and hydroquinone. The antioxidant may be one or more selected from the group consisting of ethylamine, methylamine, and hydroquinone.

As the cryoprotectant, any of the additives commonly used in the art may be used. For example, ethylene glycol and propylene glycol may be used alone or in admixture of two or more.

The heat insulating material of the present invention can be prepared by using the above-described binder resin for insulating material, and more specifically, the insulating resin without releasing harmful components of human body such as formalin and phenol-formalin. Step 1 to manufacture; Spraying the binder resin onto the glass fiber; And three steps of curing the heat insulating material of the present invention. In addition, the method may further include a step of four stages of compressing.

The composition and the composition ratio of the binder resin for the heat insulating material are the same as those described above. The two-stage glass fiber is a glass fiber commonly used in the art, and preferably includes one or two selected from glass fibers for glass wool or glass fibers for mineral wool .

If the curing temperature is less than 220 ° C., the curing is preferably carried out at 220 ° C. to 250 ° C. for 2 minutes to 10 minutes, preferably at 225 ° C. to 240 ° C. for 2 minutes to 5 minutes. There may be a problem that the physical properties such as water resistance and heat resistance may be deteriorated. If the curing temperature exceeds 250 ° C, there is a possibility that a part of the cured resin is carbonized.

The heat insulating material of the present invention can be manufactured by processing into various forms such as panel type, board type, and roll type.

The insulation material of the present invention thus produced has a compressibility of 19.5% to 25%, preferably 19.8% to 23%, when measured according to the following formula (1).

[Equation 1]

In the above equation 1, D ₁ is raised to the upper surface of the weight 20㎏ then sewn up the iron plate steel plate (length 400mm, 400mm vertically) on a test piece of width 400mm, 400mm and the vertical thickness of 50 mm, and then, after 5 minutes D _o is the mean value of the thickness of the middle part of the specimen before the weight is raised.

The insulation material of the present invention may have a water absorption rate of 6% or less, preferably 3% to 5.5%, when measured according to the following formula (2).

&Quot; (2) "

In the formula (2), M ₁ is a test specimen having a width of 200 mm, a length of 150 mm and a thickness of 50 mm, placed at a position of 30 mm below the water surface of 25 (± 5) ° C for 2 hours, will of the water and weighed after wiping with packing, M _o is the weight of the test piece before the test piece put in the water, V is the volume of water introduced around the test piece, δ is the density of water.

The heat insulating material of the present invention may have a weight retention rate of 80% to 90%, preferably 82% to 88%, when measured according to the following formula (3).

&Quot; (3) "

In Equation (3), T ₁ is a test piece having a width of 50 mm, a length of 50 mm and a thickness of 50 mm, placed at a position of 30 mm below the surface of water at 100 ° C. and allowed to stand for 2 hours. Lt; 0 > C in a vacuum oven for 3 hours, and T _o is the weight of the test piece before putting in water.

delete

As described above, the present invention can provide an environmentally friendly heat insulating material that does not emit harmful substances to human body while having excellent compression ratio, low water absorption rate, and high weight retention rate.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples should not be construed as limiting the scope of the present invention, and should be construed to facilitate understanding of the present invention.

[ Example ]

Example  1: For thermal insulation binder Copolymer  Manufacture of resin

To the flask equipped with a thermometer, a stirrer and a reflux condenser was added water, sodium persulfate (first initiator), a compound represented by the following formula 1-1, a compound represented by the formula 2, and N-methylol acrylate Amide (n-MAM) was added and stirred to prepare Mixture 1 and purged.

Separately, a dextrin mixture was prepared by adding water, dextrin (trade name DE: 19) and sodium hypophosphate (second initiator) to a flask equipped with a thermometer, a stirrer and a reflux condenser, and the mixture was heated to 80 ° C . Next, at 80 DEG C, the dextrin mixture was slowly added to the mixture 1 over 1 hour while stirring. After completion of the addition of the mixture 1, the reaction was carried out at 80 ° C for 4 hours. After completion of the reaction at the completion of the reaction, water was used to adjust the solid content of the reaction solution to 43.0 wt%, and the reaction solution was adjusted to pH 3.3 with TEA (tri-ethylamine) To prepare a copolymer resin for a heat insulating binder containing a copolymer represented by repeating units.

The composition ratios of the mixture and the dextrin mixture are shown in Table 1 below.

[Formula 1-1]

In Formula 1-1, R ¹ is a methyl group, and R ² is a hydrogen atom.

(2)

In Formula 2, R < ^{1 >} And R < ² > are each a hydrogen atom.

[Chemical Formula 6]

Wherein R ¹ is a hydrogen atom, R ² is a methyl group, and each of R ³ , R ⁴ and R ⁵ is a hydrogen atom, Is a hydrogen atom. The above X, Y and Z are the molar ratios of the monomers, and X: Y: Z = 1: 5.6: 0.24.

Example  2 ~ Example  5

A copolymer resin for a heat insulating material binder was prepared in the same manner as in Example 1 except that the copolymer resin for a heat insulating material binder was prepared at different composition ratios as shown in the following Table 1 to perform Examples 2 to 5 . The physical properties of the produced copolymer resin are shown in Table 3 below.

Example  6

A mixture 1 was prepared in the same manner as in Example 2 except that the compound represented by the following formula (1-2) was used instead of the compound represented by the formula (1-1), and the same procedure as in Example 1 was repeated to prepare a copolymer for a heat insulating material binder Resin.

The composition ratios of the mixture and the dextrin mixture are shown in Table 1 below.

[Formula 1-2]

In Formula 1-2, R ¹ is an ethyl group, and R ² is a hydrogen atom.

Classification (parts by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 dextrin
mixture dextrin 100 100 100 100 100 100 water 360 193.5 138.5 250 300 193.5 The second initiator 17 9.1 6.54 15 18 9.1 Mixture 1 water 84.3 115 84.3 84.3 82.5 115 The first initiator 2.1 2.9 2.1 2.1 2.4 2.9 The compound represented by the formula (1) 100 100 100 100 100 100 The compound represented by the formula (2) 13.45 13.22 13.45 14.50 18.30 13.22 n-MAM 20.17 20.12 20.17 30.80 25.00 20.12 Solids content 42.5
weight% 43.5
weight% 43.8
weight% 43.3 42.2 43.2
weight% 6
X, Y, Z mole ratio 1: 5.6: 0.24 1: 2.2: 0.16 1: 1.08: 0.08 1: 4.2: 0.27 1: 5.4: 0.32 1: 2.0: 0.18 Copolymer
Weight average molecular weight 24,600 30,200 32,700 28,800 25,900 39,800

Comparative Example 1

350 g of water and 15 g of sodium persulfate were charged into a flask equipped with a thermometer, a stirrer and a reflux condenser, and the temperature was raised to 80 ° C. After heating, 360 g of the compound represented by the formula (1) and 30 g of sodium persulfate were uniformly added for 2 hours. After completion of the addition, the reaction was carried out at 80 ° C for 3 hours. Next, 145 g of water was added, and the temperature was cooled to 40 ° C. 100 g of triethylamine was then added to complete the reaction to prepare an acrylic polyol binder resin having physical properties as shown in Table 4 below.

Comparative Example  2

320 g of water and 180 g of dextrin were put in a flask equipped with a thermometer, a stirrer and a reflux condenser, and 500 g of the acrylic polyol resin prepared in Comparative Example 1 was added thereto. The mixture was stirred for 30 minutes to give a starch acrylic mixture To prepare a binder resin.

Comparative Example  3

370 g of phenol, 620 g of 37% formalin, and 5 g of sodium hydroxide were charged into a flask equipped with a thermometer, a stirrer and a reflux condenser, and the temperature was raised to 70 ° C. After the completion of the reaction, the reaction was completed by neutralizing with 5 g of sulfuric acid. Thus, a phenol-formalin binder resin having physical properties as shown in Table 4 was prepared.

Comparative Example  4

A copolymer resin for a heat insulating material binder was prepared, except that 6 parts by weight of the compound represented by the formula (2) was used for 100 parts by weight of the compound represented by the formula (1), and other compositions were used in the composition and composition ratio , A copolymer resin for a heat insulating material binder was prepared in the same manner as in Example 1. The physical properties of the resin thus prepared are shown in Table 4 below.

Comparative Example  5

A copolymer resin for a heat insulating material binder was prepared, and 65 parts by weight of the compound represented by the formula (2) was used for 100 parts by weight of the compound represented by the formula (1), and other compositions were used in the composition and composition ratio shown in Table 2 below A copolymer resin for a heat insulating material binder was prepared in the same manner as in Example 1. The physical properties of the resin thus prepared are shown in Table 4 below.

Comparative Example  6

3 parts by weight of N-methylol acrylamide was used for 100 parts by weight of the compound represented by the formula (1), and other compositions were used in the composition and composition ratio shown in Table 2 below A copolymer resin for a heat insulating material binder was prepared in the same manner as in Example 1. The physical properties of the resin thus prepared are shown in Table 4 below.

Comparative Example  7

A copolymer resin for heat insulating binder was prepared by using 95 parts by weight of N-methylol acrylamide per 100 parts by weight of the compound represented by the formula (1), and other compositions were used in the composition and composition ratio shown in Table 2 below A copolymer resin for a heat insulating material binder was prepared in the same manner as in Example 1. The physical properties of the resin thus prepared are shown in Table 4 below.

Comparative Example  8

A thermoplastic resin composition was prepared in the same manner as in Example 1 except that 70 parts by weight of water was used per 100 parts by weight of the compound represented by the formula (1) To prepare a copolymer resin for a heat insulating binder. The physical properties of the resin thus prepared are shown in Table 4 below.

Classification (parts by weight) Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 dextrin
mixture dextrin 100 100 100 100 100 water 360 360 360 360 70 The second initiator 17 17 17 17 17 Mixture 1 water 84.3 84.3 84.3 84.3 84.3 The first initiator 2.1 2.1 2.1 2.1 2.1 The compound represented by the formula (1) 100 100 100 100 100 The compound represented by the formula (2) 6.0 65 13.45 13.45 13.45 n-MAM 20.17 20.17 3 95 20.17 6
X, Y, Z mole ratio 1: 5.7: 0.10 1: 5.5: 0.53 1: 5.4: 0.22 1: 5.8: 0.23 1: 5.4: 0.21 Copolymer
Weight average molecular weight 22,800 36,840 31,600 37,820 23,100

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Solid content (% by weight) 43.0 42.2 42.4 43.3 42.2 43.2 Viscosity (cps, 25 캜) 49 26 22 45 55 52 pH 3.3 3.4 3.1 3.3 3.2 3.4 Unreacted phenol (%) 0 0 0 0 0 0 Unreacted formalin (%) 0 0 0 0 0 0 Thermal decomposition rate
(600 ° C, TGA,%) 64 66 67 65 66 63

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Solid content (% by weight) 43.2 42.3 48.1 43.2 43.3 43.1 43.5 48.7 Viscosity (cps, 25 캜) 187 154 13 58 379 44 12,800 4,600 pH 3.6 5.6 7.8 3.4 3.5 3.8 4.2 3.3 Unreacted phenol (%) 0 0 0.94% 0 0 0 0 0 Unreacted formalin (%) 0 0 0.2% 0 0 0 0 0 Thermal decomposition rate
(600 ° C, TGA,%) 74 82 59 72 70 75 70 68

The results of the physical properties of the heat insulating binder resin of Tables 3 and 4 show that the comparative example 1, the comparative example 2 and the comparative example 5 have a high viscosity of 154 cps or more and a too high or low pyrolysis rate. Comparative Example 4 and Comparative Example 5 had an appropriate solid content, viscosity and pH, but the thermal decomposition rate exceeded 70%. In addition, in the case of Comparative Example 7 and Comparative Example 8, there was a problem that the viscosity was too high at 4,600 cps or more. In the case of Comparative Example 3, unreacted phenol and unreacted formalin were present.

Manufacturing example  1: Manufacture of insulation

1000 g of the copolymer resin for thermal insulation binder prepared in Example 1, 5,000 g of ionized water, 15 g of silane additive and 30 g of organic amine were added and stirred to prepare a binder resin.

Next, the glass cloth for glass wool was sprayed, the mixture was injected into an oven, and a curing process was performed at 230 ° C for 4 minutes to produce a panel-type thermal insulator.

Manufacturing example  2 to 6 and Comparative Manufacturing Example  1 to 8

A heat insulating material was prepared in the same manner as in Production Example 1 except that the same amount of each of the binder resins prepared in Production Examples 2 to 6 and Comparative Production Examples 1 to 6 was used in place of the copolymer resin of Example 1 Examples 2 to 6 and Comparative Production Examples 1 to 8 were respectively performed.

Experimental Example  : Measurement of thermal insulation properties

The compressibility, water absorption rate and water resistance of the heat insulating materials prepared in Preparation Examples 1 to 6 and Comparative Production Examples 1 to 8 were measured according to the following methods, and the results are shown in Table 5 below.

One) Compression ratio  Measure

The compressibility was measured by placing a heat insulation material having a width of 400 mm, a length of 400 mm and a thickness of 50 mm on a steel plate (400 mm in length and 400 mm in length), compressing the weight by 20 kg on the upper surface of the steel plate, Change was measured and found by the following equation (1).

[Equation 1]

In Equation (1), D ₁ is an average thickness after compression, and D _o is an average thickness before compression.

2) Absorption rate measurement

The water absorption rate is 200 mm, 150 mm, and 50 mm thick, placed at a position of 30 mm below the surface of the water in 25 (± 5) ° C, left standing for 2 hours, taking out the insulation, wiping the water on the surface of the insulation with a cloth The weight was measured, and the change in weight of the heat insulating material before and after the measurement was calculated according to the following equation (2).

&Quot; (2) "

In the above equation (2), and the weight after being introduced into the heat insulating material is M _1, and M _o is the weight prior to the heat insulating material in the water input, V is the volume of water introduced around the insulation, δ is the density of water.

3) Water resistance measurement

Water resistance A heat insulating material having a width of 50 mm, a length of 50 mm and a thickness of 50 mm was placed at a position of 30 mm below the surface of the water in a temperature of 100 ° C. and allowed to stand for 2 hours. Then, the test piece was taken out, The weight change of the heat insulating material after drying for 3 hours in a vacuum oven of 100 mmHg at a degree of vacuum of 700 mmHg was obtained by the following equation (3).

&Quot; (3) "

In Equation (3), T ₁ is the weight of the heat insulator after drying in water, and T _o is the weight of the test piece before putting in water, that is, the weight of the initial test piece.

division insulator
Appearance color Hardenability Compression ratio
(%) Absorption rate
(%) Water resistance Appearance condition Weight retention rate
(%) Manufacturing example  One Brown Good 20.1 4.3 Circular retention 84 Manufacturing example  2 Brown Good 20.2 5.0 Circular retention 86 Manufacturing example  3 Brown Good 19.9 4.4 Circular retention 85 Manufacturing example  4 Brown Good 20.5 3.8 Circular retention 83 Manufacturing example  5 Brown Good 21.7 4.7 Circular retention 86 Manufacturing example  6 Brown Good 22.2 5.2 Circular retention 88 Comparative Preparation Example 1 White Good 25.3 7 Circular retention 73 Comparative Manufacturing Example  2 Light brown Good 38.2 14 decomposition 40 Comparative Manufacturing Example  3 yellow Good 20.3 3 Circular retention 90 Comparative Manufacturing Example  4 Brown Good 21.1 8 Circular retention 70 Comparative Manufacturing Example  5 Brown Bad 34.5 6.1 Partly 58 Comparative Manufacturing Example  6 Brown Good 23.1 9.5 Partly 63 Comparative Manufacturing Example  7 Brown Can not be manufactured due to clogging of injection nozzle due to high viscosity Comparative Manufacturing Example  8 Brown Good 17.2 4.8 Circular retention 85

As shown in Table 4, it can be seen that the insulation materials of Production Examples 1 to 6 have a relatively high compression ratio as compared with Comparative Production Example 2. In Comparative Production Example 1 and Comparative Production Example 2, as compared with Production Examples 1 to 6, the absorption rate was relatively high, and the weight retention was less than 75%. In Comparative Production Example 3, it was confirmed that the insulation material of Comparative Production Example 3 had phenol-formalin in the binder resin component, and the resultant product could release the harmful substance I have a problem.

In Comparative Preparation Example 4 using less than 10 parts by weight of the compound represented by the general formula (2), it was confirmed that there was a problem that the water resistance was greatly lowered as compared with the Preparation Example 1.

In Comparative Production Example 5, there was a problem that the curability was inferior. In Comparative Production Example 6, the intermolecular crosslinking effect was low, resulting in deterioration of bonding strength between the glass fibers, resulting in a decrease in water resistance and an increase in water absorption. In Comparative Production Example 7, the degree of intermolecular bonding was too high to cause gelation, and as a result, there was a problem that the injection nozzle of the production facility was clogged and the production of the product was not desired. In Comparative Production Example 8, the solid content was 48.7% by weight, which was more than 45% by weight, resulting in a decrease in the compression ratio.

It is possible to provide a heat insulating material having excellent water resistance at the time of manufacturing a heat insulating material containing no harmful substances to a binder resin for a heat insulating material including the copolymer resin for a heat insulating material binder of the present invention It was confirmed that it is possible to produce an environmentally friendly heat insulating material that does not cause environmental hormones.

Claims (22)

A composition comprising a compound represented by the following formula (1), a compound represented by the following formula (2), a first initiator, an N-alkylol acrylamide and water; dextrin; A second initiator; And water;
The first initiator may be selected from the group consisting of sodium persulfate, Ammonium persulfate, Potassium persulfate, t-butyl hydroperoxide and sec-butyl hydroperoxide sec-butyl hydroperoxide), and more preferably,
The second initiator may be selected from the group consisting of sodium persulfate, Ammonium persulfate, Potassium persulfate, t-butyl hydroperoxide and sec-butyl hydroperoxide sec-butyl hydroperoxide). The resin composition for a heat insulating material binder according to claim 1,
[Chemical Formula 1]

Wherein R ¹ is a linear alkyl group having ¹ to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 5 to 10 carbon atoms, R ² is a hydrogen atom, A straight chain alkyl group, a C3 to C5 branched alkyl group or a C5 to C10 aryl group,
(2)

In Formula 2, R ¹ and R ² are independent and each of R ¹ and R ² is a hydrogen atom, a straight chain alkyl group having 1 to 3 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, or a C5 to C10 aryl group.
delete The heat insulating binder resin according to claim 1, wherein the N-alkylol acrylamide comprises at least one selected from N-methylol acrylamide, N-ethylol acrylamide and N-propyl acrylamide Composition.
delete The resin composition for a heat insulating material binder according to claim 1, wherein the dextrin and the mixture are contained in a weight ratio of 1: 1.2 to 5.5.
The composition according to claim 1, wherein the mixture comprises 10 to 50 parts by weight of the compound represented by the formula (2), 1 to 7 parts by weight of the first initiator, N-alkylol acrylamide 5 to 80 parts by weight and 80 to 250 parts by weight of water,
Wherein the second initiator is contained in an amount of 4 to 20 parts by weight based on 100 parts by weight of the dextrin.
A copolymer comprising a copolymer comprising a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4) and a repeating unit represented by the following formula (5);
(3)

Wherein R ¹ is a hydrogen atom, a straight-chain alkyl group of C ¹ to C 5 or a C 5 to C 10 cycloalkyl group,
[Chemical Formula 4]

Wherein R ¹ is a straight-chain alkyl group having ¹ to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 5 to 10 carbon atoms, R ² is a hydrogen atom, A branched alkyl group, a C3 to C5 branched alkyl group or a C5 to C10 aryl group,
[Chemical Formula 5]

In Formula 5, R < ^{1 >} And R ² is as independent, R ¹ And R ² are each a hydrogen atom, a straight chain alkyl group having 1 to 3 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, or a C5 to C10 aryl group.
The thermoplastic resin composition according to claim 7, wherein the copolymer comprises a repeating unit represented by the following formula (6), and the copolymer has a weight average molecular weight of 3,000 to 50,000.
[Chemical Formula 6]

Wherein R ¹ is a hydrogen atom, a straight-chain alkyl group having ¹ to 5 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms, R ² is a straight-chain alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cycloalkyl group or an aryl group of C5 ~ C10 of C10, R ^3, R ⁴ and R ⁵ as being independent, R ^3, R ⁴ and R ⁵ Each Hydrogen atom, X: Y: Z = 1: 1.0 to 6.0: 0.08 to 0.5, wherein X, Y and Z are each a linear alkyl group of C1 to C3, a branched alkyl group of C3 to C5 or an aryl group of C5 to C10, .
The thermoplastic resin binder according to claim 7, wherein the copolymer has a viscosity of 15 to 100 cps (25 DEG C) and a pH of 2.5 to 5.0.
The thermoplastic resin binder according to claim 7, wherein the copolymer has a thermal decomposition rate of 60% to 70% at 600 ° C as measured by thermogravimetry analysis.
A first step of preparing a dextrin mixture by mixing, stirring and mixing dextrin, a second initiator and water;
A step for raising the dextrin mixture to 75 ° C to 85 ° C;
A mixture comprising a compound represented by the following formula (1), a compound represented by the following formula (2), a first initiator, N-alkylol acrylamide and water is added to the dextrin mixture at 75 ° C to 85 ° C Adding and stirring, and performing a copolymer reaction to prepare a solution containing the copolymer; And
And adjusting the pH of the solution to a pH of 2.5 to 5.0 after adjusting the solid content of the solution. The method for producing a copolymer resin for a thermal insulation binder according to claim 1,
[Chemical Formula 1]

Wherein R ¹ is a linear alkyl group having ¹ to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 5 to 10 carbon atoms, R ² is a hydrogen atom, A straight chain alkyl group, a C3 to C5 branched alkyl group or a C5 to C10 aryl group,
(2)

In Formula 2, R < ^{1 >} And R ² is as independent, R ¹ And R ² are each a hydrogen atom, a straight chain alkyl group having 1 to 3 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, or a C5 to C10 aryl group.
The method of claim 11, wherein in step 4, water is added to the solution so that the solid content of the solution becomes 40% to 45%.
12. The method of claim 11 wherein in step 4 the pH is selected from the group consisting of tri- (C1-C3 alkyl) amine, ethanolamine, diethanolamine, ethylene glycol, diethylene glycol, propylene glycol , Neopentane glycol, butylene glycol, glycerin and a carbonate polyol is used to adjust the pH of the copolymer resin for a thermal insulating binder.
A binder resin for a heat insulating material characterized by comprising a copolymer resin for a heat insulating material binder according to any one of claims 7 to 10.
15. The heat insulating binder according to claim 14, wherein 0.05 to 1 part by weight of a silane additive, 0.1 to 2 parts by weight of an organic amine and 300 to 700 parts by weight of water are added to 100 parts by weight of a copolymer resin for a heat insulating material binder. Suzy.
delete A binder resin for thermal insulation according to claim 14; And glass fiber. The eco-friendly insulator excellent in water resistance.
The eco-friendly insulating material according to claim 17, wherein the compression ratio is 19.5% to 25% when measured according to the following formula (1).
[Equation 1]

In the above equation 1, D ₁ is raised to the upper surface of the weight 20㎏ then sewn up the iron plate steel plate (length 400mm, 400mm vertically) on a test piece of width 400mm, 400mm and the vertical thickness of 50 mm, and then, after 5 minutes D _o is the mean value of the thickness of the middle part of the specimen before the weight is raised.
The eco-friendly insulating material according to claim 17, wherein the water absorption rate is 6% or less when measured according to the following formula (2).
&Quot; (2) "

In the formula (2), M ₁ is a test specimen having a width of 200 mm, a length of 150 mm and a thickness of 50 mm, placed at a position of 30 mm below the water surface of 25 (± 5) ° C. and allowed to stand for 2 hours. M _o is the weight of the test piece before putting the test piece into water, V is the volume of the test piece before putting into water, and δ is the specific gravity of water.
The eco-friendly insulating material according to claim 17, wherein the weight retention is 80% to 90% when measured according to the following formula (3).
&Quot; (3) "

In Equation (3), T ₁ is a test piece having a width of 50 mm, a length of 50 mm and a thickness of 50 mm, placed at a position of 30 mm below the water surface of water at 100 ° C. and allowed to stand for 2 hours. Of the test piece after drying for 3 hours in a vacuum oven, and T _o is the weight of the test piece before putting into water.
A process for producing a binder resin comprising a copolymer resin for a heat insulating material binder, a silane additive, an organic amine and water according to any one of claims 7 to 10;
Spraying the binder resin onto the glass fiber; And
Curing at 220 DEG C to 250 DEG C for 2 minutes to 10 minutes;
The method of manufacturing an environmentally friendly insulation material according to claim 1,
22. The thermoplastic binder resin composition according to claim 21, wherein the copolymer resin for thermal insulation binders comprises a copolymer comprising a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), and a repeating unit represented by the following formula A method of producing an environmentally friendly heat insulating material excellent in water resistance;
(3)

Wherein R ¹ is a hydrogen atom, a straight-chain alkyl group of C ¹ to C 5 or a C 5 to C 10 cycloalkyl group,
[Chemical Formula 4]

Wherein R ¹ is a straight-chain alkyl group having ¹ to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 5 to 10 carbon atoms, R ² is a hydrogen atom, A branched alkyl group, a C3 to C5 branched alkyl group or a C5 to C10 aryl group,
[Chemical Formula 5]

In Formula 5, R < ^{1 >} And R ² is as independent, R ¹ And R ² are each a hydrogen atom, a straight chain alkyl group having 1 to 3 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, or a C5 to C10 aryl group.