JP7269689B2 - Formaldehyde-free molding agent for mineral wool that improves water resistance - Google Patents

Description

The present invention belongs to the field of polymer chemical materials, and more particularly to a formaldehyde-free molding agent for mineral wool that improves water resistance.

Mineral wool generally includes rock wool, glass wool and slag wool, and is lightweight, excellent heat retention, low thermal conductivity, strong heat resistance, sound insulation, waterproof, stable chemical properties, acid and base resistance, With properties such as non-corrosiveness, it is a novel lightweight insulation material. Mineral wool and its products are widely used in industrial fields such as metallurgy, construction, petroleum, chemical industry, light industry, transportation, and national defense. Although it will be expanded, its use in fields such as agriculture still has room for improvement, and its excellent thermal insulation, sound absorption and noise reduction, and fire safety properties are attracting more and more attention from various industries.

Forming agents are commonly used in the mineral wool industry. Forming agents are generally oligomeric resin aqueous solutions. By hardening and bonding the resin, the dispersed mineral wool is molded into products such as boards, felts, and wool. It provides good physical and mechanical properties to mineral wool insulation products and serves to bind the fibers together to increase the strength of mineral wool. In recent years, as the government strengthens environmental protection supervision on the insulation industry, the traditional phenolic rock wool molding agent is subject to strict regulations and even orders to stop production due to large amounts of formaldehyde and phenolic wastewater pollution. Many companies are working hard to develop more environmentally friendly and safer molding compounds to replace traditional phenolic resin molding compounds.

Patent US5661213 discloses a curable aqueous composition comprising a polyacid, a polyol and a phosphorus-containing accelerator. The composition can be used as a binder in heat-resistant nonwoven fabrics such as glass fiber nonwoven fabrics, and the binder produced from the composition has excellent bonding strength when bonding wool boards that require high properties. Because of its low strength, especially in high-temperature and high-humidity environments, it tends to sag when using wool boards, causing various inconveniences and lowering construction efficiency. Patent CN106795247A discloses a binder capable of binding glass fibers. The binder contains a polymer with a hydroxyl group, but when it comes into contact with a volatile base (aqueous ammonia solution) during use, it tends to increase in molecular weight and become unstable. there is a problem. As can be seen above, conventional formaldehyde-free polyacrylic acid-based molding agents still have some insurmountable technical problems. Among them, insufficient storage stability and bonding strength, particularly insufficient wet strength and low strength retention rate, are problems to be solved as soon as possible.

U.S. Pat. No. 5,661,213 Chinese Patent Application Publication No. 106795247

The present invention has the problem that conventional formaldehyde-free molding agents have insufficient strength, especially low wet strength, so that the properties of mineral wool produced tend to deteriorate under conditions of high temperature and high humidity. On the other hand, it provides a formaldehyde-free setting agent exclusively for mineral wool that improves water resistance, and when calculated at a solid content of 100%, it contains components with the following weight ratios.
Water-soluble resin prepolymer: 100 parts,
Polyol: 10-70 parts,
Catalyst: 2-15 parts.

Among them, the water-soluble resin prepolymer is obtained from a copolymerization reaction of monomer raw materials, and the monomer raw materials contain the following components based on the amount of substances.
a. Alkylene-bonded unsaturated carboxylic acid monomer: 90.0 to 99.0%,
b. Alkylene-bonded unsaturated hydroxy group-functional monomer: 0.5 to 5.0%,
c. Hydrophobic alkylene-bonded unsaturated monomer: 0.5-5.0%.

Preferably, the formaldehyde-free molding agent for mineral wool of the present invention contains the following weight ratios of ingredients when calculated at 100% solids content.
Water-soluble resin prepolymer: 100 parts,
Polyol: 12-50 parts,
Catalyst: 5-10 parts.

Among them, the water-soluble resin prepolymer is obtained from a copolymerization reaction of monomer raw materials, and the monomer raw materials contain the following components based on the amount of material.
a. Alkylene-bonded unsaturated carboxylic acid monomer: 92.5 to 96.0%,
b. alkylene-bonded unsaturated hydroxy group-functional monomer: 3.0 to 4.5%,
c. Hydrophobic alkylene-bonded unsaturated monomer: 1.0-3.0%.

Preferably, the number average molecular weight of the water-soluble resin prepolymer is from 500 to 30,000, preferably from 800 to 10,000, more preferably from 1,000 to 5,000. Measured using permeation chromatography (GPC) techniques. Its solids content may be 1-99%, preferably 20-60%, and the pH is 1.0-4.0.

Alkylene-linked unsaturated carboxylic acid monomers according to the present invention include acrylic acid (AA), methacrylic acid (MA), crotonic acid, fumaric acid, maleic acid (MLA), 2-methylmaleic acid, itaconic acid, 2- Among methyl itaconic acid, α-β-methyleneglutaric acid, monoalkyl maleate, monoalkyl fumarate, maleic anhydride, acrylic anhydride, methacrylic anhydride, isooctylacrylic anhydride, crotonic anhydride, or fumaric anhydride preferably one or more of acrylic acid, methacrylic acid, crotonic acid, fumaric acid, itaconic acid, or maleic acid.

Alkylene-linked unsaturated hydroxy group-functional monomers according to the present invention include, but are not limited to, (methacrylic acid) acrylic acid hydroxyalkyl ester monomers, 2-hydroxyethyl methacrylate (HEMA), acrylic acid -2-hydroxyethyl (HEA), -2-hydroxypropyl methacrylate (HPMA), -1-methyl-2-hydroxyethyl methacrylate, -2-hydroxypropyl acrylate, -1-methyl-2-hydroxy acrylate may be one or more of ethyl, 2-hydroxybutyl methacrylate, or 2-hydroxybutyl acrylate, preferably 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate is one or more of

Alkylene bond-type unsaturated hydroxy group-functional monomers can effectively improve the bond strength, particularly the dry bond strength, of the molding agent. In the present application, as a result of research, when the amount of the alkylene-bonded unsaturated hydroxy group-functional monomer added is less than 0.5% by mole, a clearly improved strength improvement effect cannot be obtained, and the amount added is It has been found that when the amount is more than 5% by mole, the viscosity of the molding agent becomes unstable and tends to gradually increase over time.

The hydrophobic alkylene-bonded unsaturated monomer described in the present invention refers to a hydrophobic alkylene-bonded unsaturated monomer that does not contain a carboxy group or a hydroxy functional group, and further effectively improves the water resistance of the molding agent, By performing a shielding effect on the hydrophilic functional groups of the molding agent, the wet strength and strength retention of the molding agent can be effectively improved. Hydrophobic unsaturated monomers according to the present invention include, but are not limited to: Acrylic acid ester-based monomers that may be methacrylic acid ester monomers, such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, methyl methacrylate, methacryl Acrylic acid ester monomers including butyl acid, isodecyl methacrylate or lauryl methacrylate, and vinyl aromatic monomers such as styrene, α-methylstyrene, p-methylstyrene, ethylvinylbenzene, vinyl It may be naphthalene, vinylxylene or vinyltoluene, a vinyl acetate monomer such as vinyl acetate or vinyl butyrate, a vinyl monomer such as vinyl alcohol, vinyl chloride, vinyl toluene, vinyl It may be benzophenone or vinylidene chloride, or other monomers capable of participating in polymerization reactions, such as acrylonitrile or glycidyl (methacrylic acid) acrylate.

Furthermore, the hydrophobic unsaturated monomers according to the invention are preferably hydrophobic unsaturated monomers having a solubility in water of 0 to 1.5 g/100 g, ethyl acrylate, n-butyl acrylate (BA ), isobutyl acrylate (i-BA), sec-butyl acrylate, tert-butyl acrylate, n-propyl acrylate (PA), cyclohexyl acrylate (CHA), lauryl acrylate, 2-ethylhexyl acrylate ( 2-EHMA), methyl methacrylate, ethyl methacrylate, n-butyl methacrylate (n-BMA), lauryl methacrylate (LMA), 2-ethylhexyl methacrylate (2-EHMA), isobornyl methacrylate (LMA), It may be one or more of styrene, α-methylstyrene, p-methylstyrene, ethylvinylbenzene, vinylnaphthalene, vinylxylene, vinyltoluene or vinyltoluene chloride.

Furthermore, the applicant believes that when the hydrophobic monomer is used, the strength and strength of the resulting molding agent can be improved by using a monomer having a lower glass transition point (Tg) of the homopolymer during synthesis (so-called soft monomer). It was found that the retention rate was further improved, and from the viewpoint of simplification of description, the Tg of the homopolymer of the monomer described in the present invention is abbreviated as the Tg of the monomer, and the Tg referred to in the present invention is GB/T29611- 2013, "Measurement of Glass Transition Point of Raw Rubber: Differential Scanning Calorimetry (DSC)", and the measurement conditions are a heating rate of 10°C/min and a nitrogen atmosphere. A possible reason, which is not bound by any theory, is that the molding agent itself of the present patent application is a product with a high cross-linking density. The advantage is that the bonding strength of the molding agent can be substantially improved. Preferred low Tg monomers/low solubility hydrophobic monomers in the present invention are hydrophobic monomers having a Tg between −15° C. and −80° C. and a solubility in water of 0 to 0.5 g/100 g. unsaturated monomers, preferably n-butyl acrylate (BA), lauryl acrylate, n-propyl acrylate (n-BA), isobutyl acrylate, 2-ethylhexyl acrylate (2-EHA) or methacryl one or more of lauryl acids;

The amount of the hydrophobic unsaturated monomer added according to the present invention is 0.5-5% molar parts, preferably 1.5-4.5% molar parts, more preferably 3.0- 4.5% mole part. When the added amount is less than 0.5% by mole, the added unsaturated water-repellent monomer does not clearly improve the water resistance, and when the added amount is greater than 5% by mole, the molding agent The crosslink density and bond strength of

Furthermore, the applicant has found that the molar ratio of alkylene-bonded unsaturated hydroxy group-functional monomer b: hydrophobic alkylene-bonded unsaturated monomer c = 1:1.5 to 1.5:1 and the content of monomer b is When it is 3.0 to 4.5 mol%, the dry strength of the molding agent is greater than 5.0 MPa, the wet strength is greater than 3.5 MPa, the strength retention rate is greater than 70%, and its viscosity increase rate is is less than 20% and has the best properties.

Polyols according to the invention are compounds with at least two hydroxy groups, 1,2-ethylene glycol, 1,3-propylene glycol, diethylene glycol, 1,4-butylene glycol, 1,2,3-cyclohexanetriol. , 1,2,4-butanetriol, 1,2,3-butanetriol, 1,2,5-pentanetriol, glycerin, glycerin polyether polyol, 2,2-dimethyl-1,3-propylene glycol, 2- Butyl-2-ethyl-1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2-methyl-2,4-butylene glycol, 1,5-pentanediol, 3-methyl-1 ,5-pentanediol, 2-methyl-2,4-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 2-ethyl-1,3-hexanediol, 2-hydroxymethyl-2-methyl -1,3-propylene glycol, 2-ethyl-2-hydroxymethyl-2-methyl-1,3-propylene glycol, 1,2,6-hexanetriol, 2,2-dihydroxymethyl-2,3-propylene glycol , pentaerythritol, trimethylolpropane, glucose, fructose, sorbitol, sucrose, mannitol, maltose, maltitol, glucose, resorcinol, catechol, pyrogallol, 1,2-ethylene glycol dimer, 1,2-ethylene glycol trimer , 1,2-propylene glycol, 1,2-propylene glycol dimer or 1,2-propylene glycol trimer. Alkanolamine polyols, which may be, for example, ethanolamine, isopropanolamine, diethanolamine, diisopropanolamine or triethanolamine, addition polymers containing at least two hydroxy groups, such as polyvinyl alcohol, partial It may also be a homopolymer or copolymer of hydrolyzed polyvinyl acetate, hydroxyethyl (methacrylic acid) acrylate or hydroxypropyl (methacrylic acid) acrylate. Further preferred polyols in the present invention are one or more of ethylene glycol, propylene glycol, glycerin, trimethylolpropane, diethanolamine, isopropanolamine, triethanolamine, polyvinyl alcohol.

Catalysts according to the present invention refer to catalysts capable of promoting the reaction of carboxylic acids with hydroxy groups, such as phosphorus-containing catalysts, such as hypophosphorous acid, hypophosphite, alkali metal hypophosphite, alkali metal phosphite, alkali metal polyphosphate, alkali metal dihydrogen phosphate, polyphosphoric acid, alkyl hypophosphite or Lewis acid, hypophosphite , e.g. sodium hypophosphite, zinc hypophosphite, potassium hypophosphite, calcium hypophosphite, magnesium hypophosphite, metal salts of inorganic acids, e.g. sodium (pyro)bisulfite or sulfite, and the Lewis acid catalyst is zinc, aluminum, zirconium, iron, magnesium, tin, titanium or boron sulfate, nitrate, halide, citrate, lactate or gluconate. may Preferred catalysts in the present invention are hypophosphites, and preferred hypophosphites are sodium hypophosphite, zinc hypophosphite, potassium hypophosphite, calcium hypophosphite, one or more of magnesium phosphites;

In the present invention, a combination of one or more of coupling agents, water repellents, and anti-dust oils may be added. Coupling agents improve the wet and wet strength of molding agents by creating a "molecular bridge" between the interface between an inorganic substance and an organic substance to tightly bond two types of materials with significantly different properties. , can improve the bonding properties of the interface, eliminate internal stress, extend the service life, and the preferred coupling agents in the present invention are epoxy siloxane coupling agents and aminosilane coupling agents. Preferred amino coupling agents or epoxy coupling agents of the invention are 3-(2,3-epoxypropoxy)propyltrimethoxysilane (KH560), 3-aminopropyltriethoxysilane (KH550), 3-(2, One or more selected from 3-epoxypropoxy)propyltriethoxysilane (KH561) or 3-(2,3-epoxypropoxy)propyldimethoxysilane, and the water repellent agent prevents adsorption of water molecules to the surface of the glass fiber. It can effectively block and improve the hydrophobicity of mineral wool, and the use of anti-dust oil in mineral wool can effectively reduce the large amount of dust scattered in the process of production, cutting, processing and transportation. can be done. Formaldehyde-free molding agent for mineral wool, coupling agent, water repellent agent, and dustproof oil are all calculated based on the solid content of 100%. added.
Formaldehyde-free molding agent for mineral wool: 100 parts,
Coupling agent: 0.1 to 5 parts, more preferably 0.2 to 1.0 parts,
Water repellent: 0 to 5 parts,
Anti-dust oil: 0-10 parts.

Furthermore, in addition to the above components, the molding agent of the present invention may optionally be appropriately watered, and adding an appropriate amount of water can reduce the viscosity, which is advantageous for transportation and use of the molding agent. As water, in general, pure water, tap water or other circulating water that does not affect the properties of the molding agent can be selected. Preferably, the amount of water added is 0-200 parts by weight per 100 parts by weight of the formaldehyde-free molding agent for mineral wool, calculated at 100% solids content.

The molding agent composition of the present invention is preferably a formaldehyde-free copolymer composition. "Formaldehyde-free" means that the composition does not contain formaldehyde and therefore does not release formaldehyde during curing, and the additives used, such as polyols and other auxiliaries, do not contain formaldehyde and therefore do not contain formaldehyde during polymerization. It does not produce formaldehyde and represents no production or release of formaldehyde during processing of the substrate.

In the present invention, in order to examine the storage stability of the molding agent, a sample is placed in a high-temperature oven and the rate of increase in viscosity (%) before and after holding at a high temperature of 60°C for 4 weeks is measured. This method can effectively examine the stability of the molding agent, and the molding agent of the present invention preferably has a viscosity increase rate of 20% or less under the holding conditions of 60° C./4 weeks. More preferably, the viscosity increase rate is 15% or less, and the viscosity increase rate (%) is 10% or less.

As a method for measuring the bond strength of the molding agent according to the present invention, it is measured according to Appendix C of the standard GB/T 34181-2017, the difference being that the premixed phenolic resin of Appendix C is added to the solid content of the molding agent such as the present invention. By changing the replacement and drying time from the conventional 180 ° C. / 20 minutes to 180 ° C. / 30 minutes, the other steps are unchanged, and the resin content is uniformly measured at 5% during measurement, and the dry state The bond strength was measured under the conditions of normal temperature 23° C./50% according to the requirements of Appendix C of the standard. In other words, the wet strength is defined as that measured after holding the prepared sample at a humidity of 90% and a temperature of 40 ° C. for 24 hours, and after the measurement is completed, the strength retention rate % = wet strength / dry strength. Further study the water resistance and moisture resistance properties of the molding agent in terms of concept.

The applicant found that the mineral wool-only molding agent described in the present application cannot be evaluated only by the conventional matrix binder property criteria in the composite material or adhesive industry, and in the composite material or adhesive industry, dry-wet Although the bonding strength is the main consideration, the method of using the molding agent according to the present invention is to coat the surface of the fiber as uniformly as possible in the form of a liquid spray, and mainly to the point contact between the fibers. This weak bond realizes the molding and properties of mineral wool, and the effect of maintaining this weak bonding force during continuous use of mineral wool is the dry strength, wet strength, and strength retention rate of the molding agent. From this point of view, it can be said that several indicators of the dry strength, the wet strength and the strength retention of the molding agent are equally important, since they are closely related to both. One major novel feature of the present invention is to balance the three indices of dry strength, wet strength, and strength retention, and the dry strength of the molding agent is greater than 4.0 MPa and the wet strength is 3.0 MPa. and the strength retention is greater than 60%, preferably the dry strength of the molding agent is greater than 5.0 MPa, the wet strength is greater than 3.5 MPa, and the strength retention is greater than 70% , By optimizing these three indicators, the resulting mineral wool product has properties that greatly exceed those of conventional acrylic acid homopolymer products, and has good high-temperature and high-humidity resistance and construction properties.

1. The formaldehyde-free mineral wool forming agent produced by the present invention does not release free formaldehyde, does not add volatile bases, and meets the requirements of eco-friendly, environmentally friendly, VOC-free and formaldehyde-free standards.
2. The mineral wool forming agent of the present invention has good stability, and the viscosity does not change significantly in a high temperature environment, and the viscosity increase rate is within 10%, so that it can be stored stably for a long time. Therefore, it is suitable for industrial use.
3. The formaldehyde-free mineral wool forming agent produced by the present invention has good dry/wet strength and water resistance at the same time, and is the best comprehensive mineral wool forming agent produced by the technical solution of the present invention As for the physical properties, the dry strength is greater than 5.0 MPa, the wet strength is greater than 3.5 MPa, and the strength retention rate is greater than 70%, greatly exceeding conventional acrylic acid homopolymer products.
4. Finally, the mineral wool board produced from the molding agent product proposed in the present invention has a hardness superior to that of the conventional acrylic acid homopolymer product, and has good water and aging resistance and construction properties.

The following clearly and completely describes the technical solutions according to the embodiments of the present invention, and the described embodiments are only some embodiments of the present invention, not all the embodiments. If a person skilled in the art obtains other embodiments without creative work based on the embodiments of the present invention, they shall all fall within the protection scope of the present invention.

The current national standards and standards referenced in the relevant tests referred to in this application are:
The method for measuring the formaldehyde content of the molding agent is according to Appendix D of the standard GB/T 34181-2017 "Molding agent for mineral wool insulation products", and the method for measuring the properties of mineral wool refers to the following standards.
GB/T 13350-2017 "Glass wool for thermal insulation and its products"
GB/T 19686-2015 "Rock wool insulation products for construction"

1. Forming agent stability measurement and bond strength test Example 1
The composition of the resin prepolymer is such that the molar ratio of acrylic acid: hydroxyethyl acrylate: butyl acrylate is 98.0: 1.0: 1.0, the number average molecular weight Mn of the resin prepolymer is 2500, and the solid Based on the content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine, and 5 parts of sodium hypophosphite catalyst are uniformly mixed by adding an appropriate amount of water, Prepared so that the solid content was 50% at once, then some samples were held in a high temperature 60 ° C environment for 4 weeks to measure the viscosity change, and another sample was 0.3 parts of KH560 coupling agent was added and mixed, and the dry-wet bond strength, strength retention, and formaldehyde content of the molding agent were measured according to national standards, respectively.

Example 2
The composition of the resin prepolymer is such that the molar ratio of acrylic acid:hydroxyethyl acrylate:butyl acrylate is 97.5:1.0:1.5, the number average molecular weight Mn of the resin prepolymer is 2500, and the solid Based on the content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine, and 5 parts of sodium hypophosphite catalyst are uniformly mixed by adding an appropriate amount of water, Prepared so that the solid content was 50% at once, then some samples were held in a high temperature 60 ° C environment for 4 weeks to measure the viscosity change, and another sample was 0.3 parts of KH560 coupling agent was added and mixed, and the dry-wet bond strength, strength retention, and formaldehyde content of the molding agent were measured according to national standards, respectively.

Example 3
The composition of the resin prepolymer is such that the molar ratio of acrylic acid: hydroxyethyl acrylate: butyl acrylate is 96.0: 1.0: 3.0, the number average molecular weight Mn of the resin prepolymer is 2500, and the solid Based on the content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine, and 5 parts of sodium hypophosphite catalyst are uniformly mixed by adding an appropriate amount of water, Prepared so that the solid content was 50% at once, then some samples were held in a high temperature 60 ° C environment for 4 weeks to measure the viscosity change, and another sample was 0.3 parts of KH560 coupling agent was added and mixed, and the dry-wet bond strength, strength retention, and formaldehyde content of the molding agent were measured according to national standards, respectively.

Example 4
The composition of the resin prepolymer is such that the molar ratio of acrylic acid: hydroxyethyl acrylate: butyl acrylate is 94.5: 1.0: 4.5, the number average molecular weight Mn of the resin prepolymer is 2500, and the solid Based on the content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine, and 5 parts of sodium hypophosphite catalyst are uniformly mixed by adding an appropriate amount of water, Prepared so that the solid content was 50% at once, then some samples were held in a high temperature 60 ° C environment for 4 weeks to measure the viscosity change, and another sample was 0.3 parts of KH560 coupling agent was added and mixed, and the dry-wet bond strength, strength retention, and formaldehyde content of the molding agent were measured according to national standards, respectively.

Example 5
The composition of the resin prepolymer is such that the molar ratio of acrylic acid:hydroxyethyl acrylate:butyl acrylate is 97.5:1.5:1.0, the number average molecular weight Mn of the resin prepolymer is 2500, and the solid Based on the content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine, and 5 parts of sodium hypophosphite catalyst are uniformly mixed by adding an appropriate amount of water, Prepared so that the solid content was 50% at once, then some samples were held in a high temperature 60 ° C environment for 4 weeks to measure the viscosity change, and another sample was 0.3 parts of KH560 coupling agent was added and mixed, and the dry-wet bond strength, strength retention, and formaldehyde content of the molding agent were measured according to national standards, respectively.

Example 6
The composition of the resin prepolymer is such that the molar ratio of acrylic acid: hydroxyethyl acrylate: butyl acrylate is 97.0: 1.5: 1.5, the number average molecular weight Mn of the resin prepolymer is 2500, and the solid Based on the content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine, and 5 parts of sodium hypophosphite catalyst are uniformly mixed by adding an appropriate amount of water, Prepared so that the solid content was 50% at once, then some samples were held in a high temperature 60 ° C environment for 4 weeks to measure the viscosity change, and another sample was 0.3 parts of KH560 coupling agent was added and mixed, and the dry-wet bond strength, strength retention, and formaldehyde content of the molding agent were measured according to national standards, respectively.

Example 7
The composition of the resin prepolymer is such that the molar ratio of acrylic acid:hydroxyethyl acrylate:butyl acrylate is 95.5:1.5:3.0, the number average molecular weight Mn of the resin prepolymer is 2500, and the solid Based on the content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine, and 5 parts of sodium hypophosphite catalyst are uniformly mixed by adding an appropriate amount of water, Prepared so that the solid content was 50% at once, then some samples were held in a high temperature 60 ° C environment for 4 weeks to measure the viscosity change, and another sample was 0.3 parts of KH560 coupling agent was added and mixed, and the dry-wet bond strength, strength retention, and formaldehyde content of the molding agent were measured according to national standards, respectively.

Example 8
The composition of the resin prepolymer is such that the molar ratio of acrylic acid: hydroxyethyl acrylate: butyl acrylate is 94.0: 1.5: 4.5, the number average molecular weight Mn of the resin prepolymer is 2500, and the solid Based on the content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine, and 5 parts of sodium hypophosphite catalyst are uniformly mixed by adding an appropriate amount of water, Prepared so that the solid content was 50% at once, then some samples were held in a high temperature 60 ° C environment for 4 weeks to measure the viscosity change, and another sample was 0.3 parts of KH560 coupling agent was added and mixed, and the dry-wet bond strength, strength retention, and formaldehyde content of the molding agent were measured according to national standards, respectively.

Example 9
The composition of the resin prepolymer is such that the molar ratio of acrylic acid: hydroxyethyl acrylate: butyl acrylate is 96.0: 3.0: 1.0, the number average molecular weight Mn of the resin prepolymer is 2500, and the solid Based on the content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine, and 5 parts of sodium hypophosphite catalyst are uniformly mixed by adding an appropriate amount of water, Prepared so that the solid content was 50% at once, then some samples were held in a high temperature 60 ° C environment for 4 weeks to measure the viscosity change, and another sample was 0.3 parts of KH560 coupling agent was added and mixed, and the dry-wet bond strength, strength retention, and formaldehyde content of the molding agent were measured according to national standards, respectively.

Example 10
The composition of the resin prepolymer is such that the molar ratio of acrylic acid:hydroxyethyl acrylate:butyl acrylate is 95.5:3.0:1.5, the number average molecular weight Mn of the resin prepolymer is 2500, and the solid Based on the content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine, and 5 parts of sodium hypophosphite catalyst are uniformly mixed by adding an appropriate amount of water, Prepared so that the solid content was 50% at once, then some samples were held in a high temperature 60 ° C environment for 4 weeks to measure the viscosity change, and another sample was 0.3 parts of KH560 coupling agent was added and mixed, and the dry-wet bond strength, strength retention, and formaldehyde content of the molding agent were measured according to national standards, respectively.

Example 11
The composition of the resin prepolymer is such that the molar ratio of acrylic acid: hydroxyethyl acrylate: butyl acrylate is 94.0: 3.0: 3.0, the number average molecular weight Mn of the resin prepolymer is 2500, and the solid Based on the content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine, and 5 parts of sodium hypophosphite catalyst are uniformly mixed by adding an appropriate amount of water, Prepared so that the solid content was 50% at once, then some samples were held in a high temperature 60 ° C environment for 4 weeks to measure the viscosity change, and another sample was 0.3 parts of KH560 coupling agent was added and mixed, and the dry-wet bond strength, strength retention, and formaldehyde content of the molding agent were measured according to national standards, respectively.

Example 12
The composition of the resin prepolymer is such that the molar ratio of acrylic acid: hydroxyethyl acrylate: butyl acrylate is 92.5: 3.0: 4.5, the number average molecular weight Mn of the resin prepolymer is 2500, and the solid Based on the content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine, and 5 parts of sodium hypophosphite catalyst are uniformly mixed by adding an appropriate amount of water, Prepared so that the solid content was 50% at once, then some samples were held in a high temperature 60 ° C environment for 4 weeks to measure the viscosity change, and another sample was 0.3 parts of KH560 coupling agent was added and mixed, and the dry-wet bond strength, strength retention, and formaldehyde content of the molding agent were measured according to national standards, respectively.

Example 13
The composition of the resin prepolymer is such that the molar ratio of acrylic acid:hydroxyethyl acrylate:butyl acrylate is 94.5:4.5:1.0, the number average molecular weight Mn of the resin prepolymer is 2500, and the solid Based on the content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine, and 5 parts of sodium hypophosphite catalyst are uniformly mixed by adding an appropriate amount of water, Prepared so that the solid content was 50% at once, then some samples were held in a high temperature 60 ° C environment for 4 weeks to measure the viscosity change, and another sample was 0.3 parts of KH560 coupling agent was added and mixed, and the dry-wet bond strength, strength retention, and formaldehyde content of the molding agent were measured according to national standards, respectively.

Example 14
The composition of the resin prepolymer is such that the molar ratio of acrylic acid: hydroxyethyl acrylate: butyl acrylate is 94.0: 4.5: 1.5, the number average molecular weight Mn of the resin prepolymer is 2500, and the solid Based on the content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine, and 5 parts of sodium hypophosphite catalyst are uniformly mixed by adding an appropriate amount of water, Prepared so that the solid content was 50% at once, then some samples were held in a high temperature 60 ° C environment for 4 weeks to measure the viscosity change, and another sample was 0.3 parts of KH560 coupling agent was added and mixed, and the dry-wet bond strength, strength retention, and formaldehyde content of the molding agent were measured according to national standards, respectively.

Example 15
The composition of the resin prepolymer is such that the molar ratio of acrylic acid:hydroxyethyl acrylate:butyl acrylate is 92.5:4.5:3.0, the number average molecular weight Mn of the resin prepolymer is 2500, and the solid Based on the content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine, and 5 parts of sodium hypophosphite catalyst are uniformly mixed by adding an appropriate amount of water, Prepared so that the solid content was 50% at once, then some samples were held in a high temperature 60 ° C environment for 4 weeks to measure the viscosity change, and another sample was 0.3 parts of KH560 coupling agent was added and mixed, and the dry-wet bond strength, strength retention, and formaldehyde content of the molding agent were measured according to national standards, respectively.

Example 16
The composition of the resin prepolymer is such that the molar ratio of acrylic acid: hydroxyethyl acrylate: butyl acrylate is 91.0: 4.5: 4.5, the number average molecular weight Mn of the resin prepolymer is 2500, and the solid Based on the content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine, and 5 parts of sodium hypophosphite catalyst are uniformly mixed by adding an appropriate amount of water, Prepare all at once so that the solid content is 50%, then some samples are kept in a high temperature 60 ° C. environment for 4 weeks to measure the viscosity change, and another sample is 0.3 parts of KH560 coupling agent was added and mixed, and the dry-wet bond strength, strength retention, and formaldehyde content of the molding agent were measured according to national standards, respectively.

Comparative example 1
The composition of the resin prepolymer is such that the molar ratio of acrylic acid:butyl acrylate is 95.5:4.5, the number average molecular weight Mn of the resin prepolymer is 2500, it does not contain hydroxyethyl acrylate, and contains no solids. Based on the amount, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine, 5 parts of sodium hypophosphite catalyst, and 0.3 parts of KH560 coupling agent are mixed, and an appropriate amount of By adding water and mixing uniformly, it was prepared all at once so that the solid content was 50%, then it was kept in an environment at a high temperature of 60 ° C. for 4 weeks and its viscosity change was measured. The dry-wet bond strength, strength retention, and formaldehyde content of the molding agent were measured according to national standards, respectively.

Comparative example 2
The composition of the resin prepolymer is such that the molar ratio of acrylic acid: hydroxyethyl acrylate is 95.5:4.5, the number average molecular weight Mn of the resin prepolymer is 2500, it does not contain butyl acrylate and contains no solids. Based on the amount, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine, and 5 parts of sodium hypophosphite catalyst are mixed uniformly by adding an appropriate amount of water, and Then, some samples were kept at a high temperature of 60 ° C for 4 weeks to measure the viscosity change, and another sample was 0 .3 parts of KH560 coupling agent were added and mixed, and the dry-wet bond strength, strength retention, and formaldehyde content of the molding agent were measured according to national standards, respectively.

Comparative example 3
The composition of the resin prepolymer is acrylic acid: hydroxyethyl acrylate molar ratio of 95.5:5.5, the resin prepolymer has a number average molecular weight Mn of 2500, does not contain butyl acrylate, and contains no solids. Based on the amount, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine, and 5 parts of sodium hypophosphite catalyst are mixed uniformly by adding an appropriate amount of water, and Then, some samples were kept at a high temperature of 60 ° C for 4 weeks to measure the viscosity change, and another sample was 0 .3 parts of KH560 coupling agent were added and mixed, and the dry-wet bond strength, strength retention, and formaldehyde content of the molding agent were measured according to national standards, respectively.

Comparative example 4
The composition of the resin prepolymer is such that the molar ratio of acrylic acid: hydroxyethyl acrylate: butyl acrylate is 99.0:0.5:0.5, the number average molecular weight Mn of the resin prepolymer is 2500, and the solid Based on the content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine, and 5 parts of sodium hypophosphite catalyst are uniformly mixed by adding an appropriate amount of water. , Prepared so that the solid content was 50% at once, then some samples were kept in a high temperature 60 ° C. environment for 4 weeks to measure the viscosity change, and another sample was , 0.3 parts of KH560 coupling agent were added and mixed, and the dry-wet bond strength, strength retention rate, and formaldehyde content of the molding agent were measured respectively according to national standards.

Comparative example 5
The composition of the resin prepolymer is such that the monomer composition is all acrylic acid, the polymer has a number average molecular weight Mn of 2500, does not contain butyl acrylate and hydroxyethyl acrylate, and is based on the solid content of 100 parts of the above A resin prepolymer, 34.5 parts of triethanolamine, and 5 parts of sodium hypophosphite catalyst are uniformly mixed with an appropriate amount of water, so that the solid content is 50% at once. Then, some samples were kept at a high temperature of 60 ° C. for 4 weeks to measure the viscosity change, and another sample was 0.3 parts of KH560 coupling agent was added and mixed, and the dry-wet bond strength, strength retention, and formaldehyde content of the molding agent were measured according to national standards.

Comparative example 6
The composition of the resin prepolymer is such that the monomer composition is all acrylic acid, the polymer has a number average molecular weight Mn of 2500, does not contain butyl acrylate and hydroxyethyl acrylate, and is based on the solid content of 100 parts of the above A resin prepolymer, 38.8 parts of triethanolamine, and 5 parts of sodium hypophosphite catalyst are uniformly mixed by adding an appropriate amount of water so that the solid content is 50% at once. Then, some samples were kept at a high temperature of 60 ° C. for 4 weeks to measure the viscosity change, and another sample was 0.3 parts of KH560 coupling agent was added and mixed, and the dry-wet bond strength, strength retention, and formaldehyde content of the molding agent were measured according to national standards. The reason for increasing the amount of triethanolamine added in Comparative Example 6 is that, when comparing Comparative Examples 5 and 3, the carboxy group content of Comparative Example 5 is about 12% higher than that of Comparative Example 3. In order to compare the effect on bond strength when the carboxy group/hydroxy group content is the same as in Comparative Example 3, the ratio of triethanolamine was increased to 12% to facilitate comparison with Comparative Example 3. .

Table 1 shows the compounding ratio of the molding agents produced in the above examples and comparative examples.

Table 2 shows the measurement results of the properties of the molding agents produced in the above examples and comparative examples.

As can be seen from the results in Tables 1 and 2, when the amount of HEA and BA added is 0.5 to 4.5% molar parts, the viscosity increase rate of the molding agent is 20% or less, and the dry strength is was greater than 4.0 MPa, the wet strength was greater than 3.0 MPa, and the strength retention was greater than 60%. Further statistics on the data of Examples 11, 12, 15 and 16 revealed that the molar ratio of alkylene-linked unsaturated hydroxy group-functional monomer b:hydrophobic alkylene-linked unsaturated monomer c = 1: The dry strength of the molding agent is greater than 5.0 MPa and the wet strength is greater than 3.5 MPa when the ratio is 1.5-1.5:1 and the content of b is 3.0-4.5 mol%. , the strength retention rate is greater than 70% and the viscosity increase rate is 20% or less, which is the best property.

2. Effect of Monomers with Different Solubilities and Tg's on Molding Agent Properties Example 17:
Based on Example 11, the other conditions were unchanged except that BA was replaced with lauryl acrylate.

Example 18:
Based on Example 11, except for replacing BA with 2-EHA, other conditions were unchanged.

Comparative Example 7:
Based on Example 11, except for replacing BA with MA, other conditions were unchanged.

Comparative Example 8:
Based on Example 11, except for replacing BA with MMA, other conditions were unchanged.

The properties of the monomers used in the Examples and Comparative Examples are shown in Table 3.

Table 4 shows the properties of the molding agents prepared in Examples and Comparative Examples.

As can be seen from the results in Tables 3 and 4, the use of monomers with different properties greatly affects the properties of the molding agent. It is disadvantageous for improving the strength and water resistance of the molding agent.

3. Effect of Different Types of Monomers on Molding Agent Properties Example 19:
Based on Example 6, except that the raw materials used and the blending ratio are different. See Table 5 for the details of the raw materials and the blending ratio.

Example 20:
Based on Example 6, except that the raw materials used and the blending ratio are different. See Table 5 for the details of the raw materials and the blending ratio.

Example 21:
Based on Example 6, except that the raw materials used and the blending ratio are different. See Table 5 for the details of the raw materials and the blending ratio.

Example 22:
Based on Example 6, except that the raw materials used and the blending ratio are different. See Table 5 for the details of the raw materials and the blending ratio.

Table 6 shows the properties of the molding agents prepared in Examples and Comparative Examples.

As can be seen from the results in Tables 5 and 6 above, within the scope supported by the present specification, other monomer raw materials and blending ratios provided by the technical solution of the present invention can be used as well. As overall characteristics of the molding agent, the viscosity increase rate is 20% or less, the dry strength is greater than 4.0 MPa, the wet strength is greater than 3.0 MPa, and the strength retention rate is 60 % has been reached.

4. Water resistance comparison test of mineral wool boards with different formulations In the test examples of the present application, mineral wool boards were produced using the formulations of the molding agents of Example 11 and Comparative Example 6 of the present application, respectively. The molding agent is calculated at 100% solids content, 100 parts of formaldehyde free molding agent is further added with 3 parts of water repellent, 6 parts of anti-dust oil, appropriate amount of water is added according to process requirements, and the process is In Test Example 1 is the same as Comparative Example 1, both are rock wool boards to be tested, Test Example 2 is the same as Comparative Example 2, both are slag wool boards to be tested, and Test Example 3 is As in Comparative Example 3, glass wool boards were tested, and the details of the parameters are shown in Table 7 below.

The mineral wool samples produced in Table 7 were cut into two groups according to national standards, one group was used as a sample before deterioration and maintenance, and the strength was measured according to the provisions of the national standards, and the other group was after deterioration and maintenance. As a sample, put it in a constant temperature and humidity chamber, hold it for 7 days under temperature and humidity conditions of 50 ± 2 ° C and 95 ± 3%, measure the strength according to the national standard, and then measure the strength before and after deterioration. and strength retention were recorded, respectively, and the data are as shown in Tables 8 and 9.

As can be seen from Tables 8 and 9, the mineral wool boards manufactured using the molding agent of the present invention are superior in strength and strength retention before and after deterioration to conventional acrylic acid homopolymer molding agents. Excellent, especially when the organic content was low, there was a clear difference in the comparative measurement results.

Claims (8)

When calculated at 100% solids content,
Water-soluble resin prepolymer: 100 parts,
Polyol: 10 to 70 parts;
Catalyst: including components in a weight blending ratio of 2 to 15 parts,
Among them, the water-soluble resin prepolymer is obtained from a copolymerization reaction of monomer raw materials, and the monomer raw materials are, on a substance basis,
a. Alkylene-bonded unsaturated carboxylic acid monomer: 90.0 to 99.0%,
b. an alkylene-bonded unsaturated hydroxy group-functional monomer: 0.5 to 5.0%;
c. Hydrophobic alkylene-bonded unsaturated monomer: 0.5 to 5.0% ,
The alkylene-bonded unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methylmaleic acid, itaconic acid, 2-methylitaconic acid, α-β-methyleneglutaric acid, and malein. one or more selected from monoalkyl acid, monoalkyl fumarate, maleic anhydride, acrylic anhydride, methacrylic anhydride, isooctylacrylic anhydride, crotonic anhydride, and fumaric anhydride;
The alkylene-bonded unsaturated hydroxy group-functional monomers include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 1-methyl-2-hydroxyethyl methacrylate, acrylic selected from acid-2-hydroxypropyl, 1-methyl-2-hydroxyethyl acrylate, 2-hydroxybutyl methacrylate, and 2-hydroxybutyl acrylate;
The hydrophobic alkylene-bonded unsaturated monomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, n-propyl acrylate, and cyclohexyl acrylate. , Lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, styrene, α-methylstyrene, p- one or more selected from methylstyrene, ethylvinylbenzene, vinylnaphthalene, vinylxylene, vinyltoluene, or vinyltoluene chloride;
The catalyst is a catalyst capable of promoting the reaction between a carboxylic acid and a hydroxy group, and is one selected from sodium hypophosphite, zinc hypophosphite, potassium hypophosphite, calcium hypophosphite, and magnesium hypophosphite. or a plurality of formaldehyde-free molding agents for mineral wool that improve water resistance. The formaldehyde-free molding agent for mineral wool that improves water resistance according to claim 1, wherein the water-soluble resin prepolymer has a number average molecular weight of 500 to 30,000. The solubility in water of the hydrophobic alkylene-bonded unsaturated monomer is 0 to 1.5 g/100 g, and the glass transition point of the homopolymer is -15 ° C. to -80 ° C., Formaldehyde-free molding agent for mineral wool that improves water resistance according to claim 1 . The hydrophobic alkylene-bonded unsaturated monomer is one or more selected from n-butyl acrylate, lauryl acrylate, n-propyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, and lauryl methacrylate. Formaldehyde-free molding agent for mineral wool to improve water resistance according to claim 3 , characterized in that The polyol according to claim 1, characterized in that the polyol is one or more selected from ethylene glycol, propylene glycol, glycerin, trimethylolpropane, diethanolamine, isopropanolamine, triethanolamine, or polyvinyl alcohol. Formaldehyde-free molding agent for mineral wool that improves water resistance. When calculated at 100% solids content,
Water-soluble resin prepolymer: 100 parts,
Polyol: 12 to 50 parts;
Catalyst: including components in a weight blending ratio of 5 to 10 parts,
Among them, the water-soluble resin prepolymer is obtained from a copolymerization reaction of monomer raw materials, and the monomer raw materials are, on a substance basis,
a. Alkylene-bonded unsaturated carboxylic acid monomer: 92.5 to 96.0%,
b. an alkylene-bonded unsaturated hydroxy group-functional monomer: 3.0 to 4.5%;
c. Hydrophobic alkylene-bonded unsaturated monomer: The formaldehyde for mineral wool that improves water resistance according to any one of claims 1 to 5 , characterized by containing a component of 1.0 to 3.0%. Free molding agent. According to claim 6 , characterized in that the molar ratio range of said alkylene-bonded unsaturated hydroxy group-functional monomer and hydrophobic alkylene-bonded unsaturated monomer is 1:1.5 to 1.5:1. A formaldehyde-free molding agent specifically for mineral wool that improves water resistance as described. When calculated at 100% solids content,
Formaldehyde-free molding agent for mineral wool: 100 parts;
Coupling agent: 0.1 to 5 parts,
Water repellent agent: 0 to 5 parts,
Dustproof oil: 0 to 10 parts,
Water: 0 to 200 parts by weight of ingredients,
Among them, the coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane (KH560), 3-aminopropyltriethoxysilane (KH550), 3-(2,3-epoxypropoxy)propyltriethoxy Formaldehyde-free for mineral wool to improve water resistance according to claim 1, characterized in that it is one or more selected from silane (KH561), or 3-(2,3-epoxypropoxy)propyldimethoxysilane molding agent.