JP3455704B2 - Method for producing modified phenolic resin reinforced with poly (alkylene oxide) - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a modified phenolic resin .
The present invention relates to a manufacturing method . More specifically, it relates to a method for producing a modified phenolic resin reinforced with poly (alkylene oxide).

[0002]

2. Description of the Related Art Conventional resins used in a pulling process for producing fiber reinforced resin composites are thermosetting resins such as unsaturated polyester resins and epoxy resins. Phenolic resins, which are known to have excellent mechanical properties and electrical properties especially at high temperatures, have been used in the production of fiber reinforced products by the prepreg method, the compound method, the reaction injection molding method or the drawing method, Phenolic resin, which is conventionally used as a binder in the molding of fiber-reinforced composite products, is a by-product (moisture) that causes brittleness that causes low bondability with fibers, its slow curing property, and bubble defects compared to other resins. Not very common for. Therefore, it is necessary for the composite industry to improve the quality of drawn fiber reinforced phenolic resin composites.

Various methods have been developed to strengthen phenolic resins. For example, milling oil is used in US Pat. No. 2,267,390, rosin is used in Japanese Patent Publication No. 29-7595, and alkylphenol is used in US Pat. No. 2,675,335 to strengthen phenolic resins. US Pat. No. 4,125,502
Vinyl acetate is used in U.S. Pat.
No. 57,324 uses a highly orthoetherified resol type phenolic resin. However, all of these methods require a modifier which reacts with the phenolic resin for a certain period of time in order to obtain the desired strengthening effect.

Since meta-hydroxyphenol catalysts are currently used to reduce the gel time of phenolic resins, they can be used in the production of fiber reinforced composite products. However, the addition of the metahydroxylphenol catalyst also reduces the storage stability of the phenolic resin and the pot life of the phenolic resin.

It is well known that the binding force between the phenol resin and the surface of ordinary fibers is weak, and a filament having a special surface treatment is necessary for processing the fiber reinforced phenol resin. For example, filaments having a special surface treatment with an isocyanate coupling agent are available from glass fiber manufacturing companies (for example, Clark-Schwe).
bel Fiberglass Corp. , USA
etc). Filaments that have been subjected to these special treatments require additional equipment and manufacturing costs, and further require an operation for modifying different fibers.

US Pat. No. 5,559,197 discloses a modified phenolic resin reinforced with a phenoxy resin, and the modified phenolic resin is produced by the following steps. That is, the weight average molecular weight of 10,000 to
1,000,000 phenoxy resin and phenol are mixed at a weight ratio of phenoxy resin: phenol = 1.5: 1 to 1: 1 at an elevated temperature to form an adhesive mixture, and the adhesive mixture is mixed with an acid catalyst. To obtain a modified phenolic resin by mixing the viscous mixture with a resole-type phenolic resin, in which case the resole-type phenolic resin is 60-7
It has a solids content of 5% by weight and a free aldehyde content of 5-10% by weight, the amount of acid catalyst mixed with respect to the resole phenolic resin is 2-10% by weight, and the phenoxy resin mixed is 3%. ~ 25% by weight.

Poly (alkylene oxide) such as poly (ethylene oxide) (PEO) is a highly crystalline and water-soluble polymer. A preferred method for producing this polymer is to use alkaline earth metals (Ca, Ba and S).
It includes the polymerization of alkylene oxides via a coordination polymerization mechanism that is acted by the oxide of the salt of r) as a catalyst or a cocatalyst formed by an organometallic compound and water. Specific examples of PEO use include water-soluble packaging films,
It is a blend for producing surfactants, sizing agents, gelling agents, thickening agents, biomedical substances and conductive polymers.

According to the knowledge of the present inventors, there is no prior art suggesting the use of poly (alkylene oxide) for strengthening the phenolic resin and simultaneously strengthening the bond between the phenolic resin and the fiber.

[0009]

The first object of the present invention is to provide a method for producing a modified resol type phenolic resin and a modified novolak type phenolic resin reinforced by poly (alkylene oxide).

[0010]

Manufacturing method of the modified resole type phenolic resin according to the present invention, in order to solve the problems] consists following steps.

Strengthened by poly (alkylene oxide)
The method for producing the modified resol type phenolic resin,
(A) (a) poly (alkylene oxide) and
(B) Phenol (a): (b) = 1.5: 1 to 1:
Mix at elevated temperature in a weight ratio of 1 to form a viscous mixture
And (B) mixing the viscous mixture of step (A) with acid catalyst (c)
Viscous mixture having a relatively lower viscosity than the viscous mixture.
The step of obtaining a compound, and (C) the viscous mixture of step (B)
Modified resol type phenolic resin mixed with resin (d)
And a resol-type phenol resin.
The amount of the acid catalyst (c) mixed with (d) is 2 to 1
0% by weight and also mixed with poly (alkyleneoxy)
The amount of side) (a) is 2 to 10% by weight.

In the above method, the elevated temperature is 100 ° C.
And the poly (alkylene oxide) is poly (ethylene oxide)
Ren oxide), poly (propylene oxide)
Is poly (ethylene oxide) and poly (propylene oxide)
Side), especially the poly (alkylene)
Cide) is poly (ethylene oxide)
preferable.

In the above method, the poly (alkylene)
Cyside) and phenol in a 1: 1 weight ratio.
And the amount of the poly (alkylene oxide) mixed is
4 to 8% by weight based on the resol type phenolic resin
And the amount of the acid catalyst mixed is the resol-type pheno
It is preferably 5% by weight based on the weight of the resin.

In the above method, guanidine as a promoter is mixed before the acid catalyst is mixed with the viscous mixture of step (A), the amounts of guanidine and the acid catalyst are the same , and the guanidine is diphenyl. Is guanidine,
The acid catalyst is preferably selected from the group consisting of p-toluenesulfonic acid, phenolsulfonic acid, benzoic acid and phosphoric acid.

In the above method, the phenol is pheno
, Orthocresol, metacresol, paracrezo
, Dimethylphenol, ethylphenol, paraffin
Phenylphenol, para-butylphenol, para-penti
Ruphenol, Bisphenol-A and Metadihydro
Be selected from the group consisting of xylbenzene
preferable.

In the above method, (a) poly (alkyle)
Weight average molecular weight of 100,000-
8,000,000, (d) Resol type phenolic resin
Has a solid content of 60 to 75% by weight and a free aldehyde content
5 to 10% by weight, and the amount of component (b) is the weight of component (d).
It is preferably 2 to 15% with respect to the amount.

The present inventors have found that the tackiness in step (A)
The viscosity of the mixture is sufficiently reduced by the addition of acid catalyst.
It was surprising to find that. The acid catalyst is
In the viscous mixture, poly (alkylene oxide) is charged.
Results in cargo transport and, consequently, in polar phenolic solvents
The solubility of poly (alkylene oxide)
Side) to promote the distribution of resol type phenolic resin
It seems to be one .

Considering the functionality or operability,
Equivalent to acid catalysis for the purposes of clarity is to catalyze
It is an electrolyte that has.

Modified novolac type phenol according to the present invention
The resin manufacturing method includes the following steps. (A ′) (a) poly (alkylene oxide) and
(B) Phenol (a): (b) = 1.5: 1 to 1:
Mix at elevated temperature in a weight ratio of 1 to form a viscous mixture
The step (B ') and the step (A') viscous mixture are treated with a novolac
Modified novolac type ferrite mixed with the nol resin (d ')
Novolac type flux
Poly (alkoxy) mixed with enol resin (d ')
The amount of poly (ene oxide) is 2 to 10% by weight.
Modified novolaks reinforced by (rubylene oxide)
Of producing type phenolic resin.

In the above method, the elevated temperature is 100 ° C.
In addition, the curing agent (C ') is changed from the step (B').
Novolac type phenolic resin mixed with
Amount of the curing agent relative to the weight of the type phenolic resin (d ')
Is 2 to 15% by weight, and the amount of the curing agent is component (d ').
Is preferably 10% with respect to the weight of.

In the above method, the curing agent is hexamethyi.
Rentetramine, S-triamine and trimethylol
Selected from the group consisting of phosphine oxides
In particular, the curing agent is hexamethylenetetramine,
The poly (alkylene oxide) is poly (ethylene oxide)
Side), poly (propylene oxide) or poly
(Ethylene oxide) and poly (propylene oxide)
And a poly (alkylene oxide)
Id) is preferably poly (ethylene oxide)
Good

In the above method, the poly (alkylene)
Cyside) and phenol in a 1: 1 weight ratio.
And the amount of the poly (alkylene oxide) mixed is
4 to 8% by weight with respect to the novolac type phenol resin
And the phenol is phenol, ortho-cresol
, Meta-cresol, para-cresol, dimethylpheno
Alcohol, ethylphenol, paraphenylphenol,
Labylphenol, parapentylphenol, bisphenol
Consisting of Enol-A and metadihydroxybenzene
It is preferably selected from the group.

In the above method, the (a) poly (alkyne
Lenoxide) weight average molecular weight of 100,000 to
8,000,000, (d ') novolac type phenol
The viscosity of the resin at 25 ° C is 200 to 2,000 cp
s, preferably a viscosity at 25 ° C of 300 cps
Comprising the amount of component (b) relative to the weight of component (d ').
It is preferably 2 to 15%.

The poly (alkylene oxide) (d ')
Has excellent adhesive properties, so that when it is directly mixed with the novolac type phenolic resin (d ') used in the present invention, it produces a sticky dough-like mixture.
The resulting sticky dough-like mixture is a composite material,
It cannot be further processed in the processing of coating compositions or adhesives and is therefore useless. In order to produce the desired novolac type phenolic resin reinforced with poly (alkylene oxide), the poly (alkylene oxide) (d ') must be mixed with phenol at elevated temperature in step (A'). I won't. It should be noted that commercially available novolac resins having a higher viscosity (average molecular weight) than the novolac type phenolic resin (d ') used in the present invention cannot be used in the present invention.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides a method for producing a modified phenolic resin reinforced with poly (alkylene oxide).
It is intended to be provided . Both resole type phenolic resins and novolac type phenolic resins may be toughened with poly (alkylene oxide) according to the present invention.

Phenolic resins are hard due to their bulky benzene rings. However, phenolic resins are brittle due to the gaps that exist between the benzene rings. In the present invention, the hydrogen bond between the hydroxyl groups of the poly (alkylene oxide) and the phenolic resin (excellent compatibility) and the long flexible chains of the poly (alkylene oxide) cause the gap to fill. Due to the reduction in free volume, the poly (alkylene oxide) successfully strengthens the phenolic resin. The long, flexible chains of poly (alkylene oxide) present therein increase the amount of energy absorbed and, because of the external forces exerted on the modified phenolic resin, extend the process of disintegration. is there.

The ether groups of poly (alkylene oxide) also provide a bond between the phenolic resin and the substrate when the modified phenolic resin is used in coating compositions, adhesives or fiber reinforced resin composites. Strengthen. Furthermore, when the modified phenolic resin is used as a binder during the processing of the fiber-reinforced resin composite, the poly (alkylene oxide) not only enhances the wettability of the fiber, but also acts as a lubricant.

A preferred method for producing the resol type phenolic resin (d) used in the present invention is carried out by condensing an excess amount of formaldehyde and the like with phenol in the presence of an alkaline catalyst. This method is known to those of skill in the art, as described in US Pat. No. 4,419,400, the disclosure of which is included herein by reference.

Acid catalysts are described in British Patent No. 1,363,277.
No. 6,058,049, which includes organic acid catalysts disclosed in US Pat. Preferred catalysts are p-toluenesulfonic acid, phenolsulfonic acid,
It is selected from the group consisting of benzoic acid and phosphoric acid. The amount of acid catalyst used is from 2 to 10% by weight, preferably about 5% by weight, based on the weight of the resol type phenolic resin.

The acid catalyst (c) may be used with a promoter such as guanidine, preferably diphenylguanidine, the amount of guanidine being approximately the same weight as the amount of acid catalyst.

In one of the preferred embodiments of the present invention, the poly (alkylene oxide) and phenol are:
Mixed and stirred at 100 ° C to form a sticky material, into which a mixture of p-toluenesulfonic acid and diphenylguanidine was added at 100 ° C with stirring.
A viscous mixture was obtained with a viscosity at 250C of 250 cps. The viscous mixture was added to the resol type phenolic resin heated to 100 ° C., and the resulting mixture was well stirred to obtain the modified resol type phenolic resin according to the present invention. This modified resol type phenolic resin is 30 ℃
It had a viscosity of 800-2,000 cps after cooling to. This viscosity was measured using a Brookfield viscometer according to the method of ASTM D2393.

The preferred method for producing the novolac type phenolic resin (d ') used in the present invention is to carry out the condensation reaction for a certain period of time in the presence of an acidic catalyst at a molar ratio of formaldehyde or the like and phenol of 1: 0.8. , An alkali is added to neutralize the reaction mixture, the aqueous layer and the organic layer are separated, and water and small molecules in the organic layer are removed by evaporation. In a preferred embodiment of the invention, the condensation reaction is carried out at 100 ° C. for 30 minutes and the novolac type phenolic resin produced has a number average molecular weight of about 492 and a weight average molecular weight of about 2,032. ing.
In addition, the novolac-type phenolic resin produced has a solids content of about 90% by weight and a free phenol content of about 0.15% by weight, which represents the bond between the two phenolic rings through the methylene bond. 19% is ortho-ortho, 57% of which is ortho-para or 24% of which is para-para.

In another preferred embodiment of the invention,
Poly (alkylene oxide) and phenol were mixed and stirred at 100 ° C. to obtain a sticky substance. 10
Novolak type phenolic resin manufactured at 0 ℃ or higher,
This viscous mixture was added, and the resulting mixture was stirred well and left at 80 ° C. for 30 minutes or longer to obtain the novolac type phenol resin of the present invention. This modified novolac type phenolic resin has a temperature of 200 to 2,000 after being cooled to 25 ° C.
It had a viscosity of cps.

The novolak type phenolic resin is a low molecular weight resin because an excess amount of phenol is usually used for the reaction with an aldehyde in its synthesis, and the synthesized novolac type phenolic resin is a macromolecular compound. Reactive methanol group (--CH ₂ O) for growing a compound
This is because H) is not included. A curing agent such as hexamethylenetetramine must be added to crosslink the novolac type phenolic resin, resulting in the formation of a cured network.

Most novolac type phenolic resins available on the market are in powder form and are not suitable for use in the drawing process for producing fiber reinforced phenolic resin composites. A novolak phenolic resin in solution is also commercially available, which has about 14 wt% organic solvent and 86 wt% solids. The organic solvent is
Volatilizes during the drawing process of the fiber-reinforced phenolic resin composite, damaging the environment. The liquid novolac type phenolic resin is produced by the present inventors, water by-produced is removed in a furnace under reduced pressure, and then impregnated into fibers in a drawing method to be used directly.

Suitable phenols used in the present invention include phenol, orthocresol, metacresol, paracresol, dimethylphenol, ethylphenol, paraphenylphenol, parabutylphenol, parapentylphenol, bisphenol-A, metadihydroxybenzene. However, the present invention is not limited to these.

As is well known in the art, inorganic fillers such as talc, silica, clay, etc. may be added to the liquid resin to improve the mechanical properties of the pultruded composite. The amount of the inorganic filler added is 10 to 20% by weight based on the weight of the modified phenolic resin.

The modified phenolic resin can be used at least in the production of coating compositions, adhesive compositions and fiber reinforced resin composites. In each of its uses, the modified phenolic resin used produces a very small amount of water as a by-product during cross-linking, thus reducing the amount of pores due to water evaporation, which results in toughness and mechanical properties of the final product. Properties are significantly improved.

[0039]

EXAMPLES The present invention is explained in more detail by the drawing method in the following examples, where "parts" and "%" are by weight unless otherwise specified.

[0040] Example 1 Poly (ethylene oxide) (PEO) Adjustment modified resole type phenolic resin reinforced modified Les Orres type phenolic resin by was prepared according to the formulations listed in Table 1 below.

[0041]

[Table 1]

8 g of poly (ethylene oxide) and 8 g of phenol were mixed and stirred at a temperature of 100 ° C. under a nitrogen atmosphere for 1 hour to obtain a miscible adhesive material. 5 g of p-toluenesulfonic acid and 5 g
Of diphenylguanidine were mixed and stirred under reduced pressure at 100 ° C. for 30 minutes, and then the adhesive material was added. The resulting mixture was thoroughly stirred for about 30 minutes to give a solution with a viscosity at 100 ° C. of about 250 cps . This solution was added to 100 g of the resole-type phenolic resin kept at 100 ° C. in a furnace, while being gently stirred to form a mixed viscous solution.

The above method was applied to poly (ethylene oxide).
Except that the weight of the resol type phenolic resin was changed (parts per hun).
dred parts of resin by we
modified resol type phenolic resin products with different percentages of poly (ethylene oxide) based on light, phr).

Example 2 Preparation of modified novolac type phenolic resin reinforced with poly (ethylene oxide) (PEO) Modified novolac type phenolic resin was prepared according to the formulation shown in Table 2 below.

[0045]

[Table 2]

1,694 g (18 mol) of phenol and 1,217.5 g of formaldehyde aqueous solution (35
3% in a 5.0-liter three-necked flask containing dilute aqueous sulfuric acid solution (4 g of H ₂ SO _{4 in} 20 ml of water) as a catalyst.
The reaction was allowed for 0 minutes. The reaction mixture was neutralized with NaOH (aq) and the neutralized reaction mixture separated from the aqueous layer. Then, the remaining water and small molecules were evaporated from the organic layer under reduced pressure to obtain a liquid novolac type phenol resin having a viscosity of about 300 cps at 25 ° C.

The novolac phenolic resin prepared has a number average molecular weight of about 492 and a weight average molecular weight of about 2032 by GPC analysis. Furthermore, the prepared novolac type phenolic resin was analyzed,
Having about 90 wt% solids and about 0.15 wt% free phenol, the bond between the two phenol rings via a methylene bond is 19% ortho-ortho,
57% is ortho-para and 24% is para-para.

8 g of poly (ethylene oxide) and 8 g of phenol were mixed and stirred under a nitrogen atmosphere at 100 ° C. for 1 hour to obtain a miscible adhesive material. Then, this miscible adhesive material was added to 100 g of the above-prepared novolac-type phenolic resin, stirred while the mixture was left standing in an oven at 80 ° C. for 30 minutes to obtain a low viscosity such as water. A solution of Then 10g
Hexamethylenetetramine was added to this low-viscosity solution to obtain an impregnated resin used in the subsequent drawing method.

The above method was applied to poly (ethylene oxide)
A modified novolac type phenolic resin product having different percentages of poly (ethylene oxide) based on novolac type phenolic resin (phr) was prepared in the same manner except that the weight of was varied.

Example 3 Extraction Method The modified phenolic resin prepared by the above method was placed in an impregnation tank and kept at room temperature of 30 ° C. 764-NT-21
Twenty rovings of 8 glass fibers were pulled into a bath of impregnating resin maintained at 30 ° C. 764-NT-218 glass fiber has a specific gravity of 2.54, and also 1% of this fiber.
The strands of the book have a diameter of 13.1 μm and 2.2 × 1
It has a tensile strength of 0 ⁵ psi. Impregnated glass fiber roving removes excess resin and air through a throttling orifice, length 82 cm, width 1.27 cm,
It was passed through a 0.33 cm thick curing die. Two sets of individually controlled electric plate heaters were installed on the top and bottom of the die, the first and second sets of plate heaters had a length of 30 cm, the temperature was 220 ℃ and 240 ℃ respectively. Is. The drawing speed was fixed at 30 cm / min. The final pultruded composite product had a fiber content of 60% by volume when the modified resol type phenolic resin was used and a fiber content of 70% by volume when the modified novolac type phenolic resin was used.

The final pultruded composite was further post-cured at a temperature of 180 ° C. for 1 hour.

The glass fiber reinforced modified phenolic resin composites drawn with modified phenolic resins having different phenolic resin contents by the above-mentioned method were tested according to ASTM D790, ASTM with and without post-curing.
D256, ASTM-2863 and UL-94 and tested for its flexural modulus, notched Izod impact strength, L.S. O. I. (Extreme oxygen index) and flame retardancy (94V-0, 94V-1 or 94V-2) were obtained, respectively. The results are shown in Tables 3 and 4.

[0053]

[Table 3]

[0054]

[Table 4]

[0055]

As is apparent from Table 3, the flexural modulus and impact strength of the glass fiber / modified phenolic resin composites with and without post-curing are determined by the poly (ethylene oxide) per weight (phr) of the phenolic resin. The glass fiber / modified phenolic resin composite prepared by the modified phenolic resin containing 6% by weight of poly (ethylene oxide) has the highest flexural modulus and impact strength. ing.
These results indicate that blending a small amount of poly (ethylene oxide) with the phenolic resin has a good reinforcing effect. Furthermore, these results also indicate that post-cure sufficiently improves the mechanical properties of the glass fiber / modified phenolic resin composite.

The UL-94 and L. O. I. The results of the tests show that the glass fiber / modified phenolic resin composite is an excellent flame retardant material with good flame retardancy and low smoke volume.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Bibliography Zhikai Zhong, Qipe ng Guo, Crosslinkable Interpolymers Complexes of Novolacic reinsurance and Pour (et hillene oxy urine, Pour), et al. Year, Vol. 36, pp. 401-411 Peter P. Chu, Hew- Der Wu, Chih-tsung Lee, Thermodaynamic Properties of Nov olac-Type Phenolic Resin Blended wit h Poly (ethylene ox ide), Journal of Po lymer Science: Part B: Polymer Physic s, 1998 years, Vol. 36, pp. 1647-1655 (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 8/28-8/36 C08L 61/00-61/34 C08L 71/02-71/03

Claims (25)

(57) [Claims] 1. (A) (a) poly (alkylene oxide) and (b) phenol (a) :( b) = 1.
Mixing at elevated temperature in a weight ratio of 5: 1 to 1: 1 to form a tacky mixture; (B) mixing the tacky mixture of step (A) with an acid catalyst (c). Comprising a step of obtaining a viscous mixture having a relatively lower viscosity than the viscous mixture, and (C) mixing the viscous mixture of step (B) with the resole phenolic resin (d) to form a modified resole phenolic resin. The amount of the acid catalyst (c) mixed with the resol type phenol resin (d) is 2 to 1
A method for producing a modified resol-type phenolic resin reinforced by poly (alkylene oxide), which is 0% by weight and the amount of poly (alkylene oxide) (a) mixed is 2 to 10% by weight. 2. The method according to claim 1, wherein the elevated temperature is 100 ° C. 3. The method according to claim 1, wherein the poly (alkylene oxide) is poly (ethylene oxide), poly (propylene oxide) or a mixture of poly (ethylene oxide) and poly (propylene oxide). 4. The method of claim 3, wherein the poly (alkylene oxide) is poly (ethylene oxide). 5. The method according to claim 1, wherein the poly (alkylene oxide) and the amount of phenol are mixed in a weight ratio of 1: 1. 6. The method according to claim 1, wherein the amount of the poly (alkylene oxide) mixed is 4 to 8% by weight based on the resole type phenolic resin. 7. The amount of the acid catalyst mixed is 5% by weight based on the weight of the resol-type phenol resin.
The method described in. 8. The method of claim 1, wherein guanidine as a promoter is mixed before the acid catalyst is mixed with the viscous mixture of step (A) and the amounts of guanidine and the acid catalyst are the same. . 9. The method of claim 8, wherein the guanidine is diphenylguanidine. 10. The method according to claim 1, wherein the acid catalyst is selected from the group consisting of p-toluenesulfonic acid, phenolsulfonic acid, benzoic acid and phosphoric acid. 11. The phenol is phenol, orthocresol, metacresol, paracresol, dimethylphenol, ethylphenol, paraphenylphenol, parabutylphenol, parapentylphenol,
The method according to claim 1, which is selected from the group consisting of bisphenol-A and metadihydroxybenzene. 12. (a) Poly (alkylene oxide)
Has a weight average molecular weight of 100,000 to 8,000,00.
0, (d) Resol-type phenol resin has a solid content of 60-
75% by weight and 5-10% by weight of free aldehyde, and the amount of component (b) is 2-1 with respect to the weight of component (d).
It is 5%, The method of any one of Claims 1-11. 13. (A ′) (a) poly (alkylene oxide) and (b) phenol (a) :( b) =
A weight ratio of 1.5: 1 to 1: 1 is used to mix the mixture under elevated temperature to form a viscous mixture, and (B ') the viscous mixture of step (A') is mixed with a novolac type phenol resin (d). ') To form a modified novolac type phenolic resin, the novolac type phenolic resin (d')
The amount of poly (alkylene oxide) mixed with the poly (alkylene oxide) is 2 to 10% by weight.
Of a modified novolak type phenolic resin reinforced by the method described above. 14. The elevated temperature is 100 ° C.
The method according to 3. 15. A curing agent (C ′) is further added in the step (B ′).
14. The method according to claim 13, wherein the amount of the curing agent is 2 to 15% by weight based on the weight of the novolak type phenolic resin (d ′) when mixed with the modified novolak type phenolic resin. 16. The method according to claim 15, wherein the amount of the curing agent is 10% based on the weight of the component (d ′). 17. The curing agent is selected from the group consisting of hexamethylenetetramine, S-triamine and trimethylolphosphine oxide.
The method described in. 18. The method of claim 17, wherein the curing agent is hexamethylenetetramine. 19. The method of claim 13, wherein the poly (alkylene oxide) is poly (ethylene oxide), poly (propylene oxide) or a mixture of poly (ethylene oxide) and poly (propylene oxide). 20. The method of claim 19, wherein the poly (alkylene oxide) is poly (ethylene oxide). 21. The amount of poly (alkylene oxide) and phenol are mixed in a weight ratio of 1: 1.
The method described in. 22. The method according to claim 13, wherein the amount of the poly (alkylene oxide) mixed is 4 to 8% by weight based on the novolac type phenolic resin. 23. The phenol is phenol, orthocresol, metacresol, paracresol, dimethylphenol, ethylphenol, paraphenylphenol, parabutylphenol, parapentylphenol,
14. The method according to claim 13, which is selected from the group consisting of bisphenol-A and metadihydroxybenzene. 24. (a) Poly (alkylene oxide)
Has a weight average molecular weight of 100,000 to 8,000,00.
The viscosity of the 0, (d ') novolac type phenolic resin at 25 ° C is 200 to 2,000 cps, and the amount of the component (b) is 2 to 15% based on the weight of the component (d'). The method according to any one of 1. 25. The method according to claim 24, wherein the novolac type phenolic resin (d ′) has a viscosity at 25 ° C. of 300 cps.